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Numéro de publicationCN100591711 C
Type de publicationOctroi
Numéro de demandeCN 200510022997
Date de publication24 févr. 2010
Date de dépôt25 juil. 2002
Date de priorité26 juil. 2001
Autre référence de publicationCN1789328A, CN1800243A, CN100443542C, US6780916, US20030027912, WO2003010225A1
Numéro de publication200510022997.1, CN 100591711 C, CN 100591711C, CN 200510022997, CN-C-100591711, CN100591711 C, CN100591711C, CN200510022997, CN200510022997.1
InventeursD·董, E·斯森, R·莱康拜
DéposantM&G聚合物意大利有限公司
Exporter la citationBiBTeX, EndNote, RefMan
Liens externes:  SIPO, Espacenet
Containers with low haze
CN 100591711 C
Résumé
Provided is a container which provides effective oxygen-scavenging functionality prepared by the oxygen-scavenging resin combination and has low haze.
Revendications(28)  Langue du texte original : Chinois
1.一种具有至少一个壁的容器,其中所述壁包含聚集区,其中所述聚集区包含以下组分: 成膜聚合物,所述聚合物包括聚酯;和包含有效量氧清除粒子的粒子群,其中所述群的粒子数量不超过以下浓度: (6x107粒子÷T)/立方厘米聚合物其中T为所述聚集区的厚度,以mil表示;并且其中所述壁的透射Hunter雾度最高为每mil容器壁1%。 A container having at least one wall, wherein said wall comprises enclave, wherein said gathering area contains the following components: a film-forming polymer, said polymer comprising polyester; and comprising an effective amount of oxygen-scavenging particles particle group, wherein the number of particles of said population does not exceed the following concentrations: (6x107 particles ÷ T) / cubic centimeter polymer wherein T is the thickness of the accumulation zone to represent mil; and a transmission Hunter haze wherein the wall up to 1 percent per mil of the container wall.
2. 权利要求1的容器,其中所述聚酯包括线性聚酯。 2. The container of claim 1, wherein said polyester comprises linear polyester.
3. 杈利要求2的容器,其中所述聚酯包括聚对苯二甲酸乙二醇酯、聚对苯二甲酸乙二醇酯的共聚物、聚萘二甲酸乙二醇酯、聚萘二甲酸乙二醇酯的共聚物、聚对苯二甲酸丁二醇酯、聚对苯二甲酸丁二醇酯的共聚物、聚对苯二曱酸丙二醇酯或聚对苯二甲酸丙二醇酯的共聚物。 3. prong receptacle claims 2, wherein said polyester comprises polyethylene terephthalate, polyethylene terephthalate copolymers, polyethylene naphthalate polyethylene terephthalate, polyethylene naphthalate copolymer of polyethylene terephthalate, polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate, polybutylene terephthalate, poly terephthalic acid propylene glycol ester 曱 or polyethylene terephthalate glycol ester copolymer thereof.
4. 权利要求1的容器,其中所述聚酯用一种或多种多官能团共聚单体制备。 4. The container of claim 1, wherein said polyester with one or more polyfunctional comonomers.
5. 权利要求4的容器,其中所迷多官能团共聚单体选自均苯四曱酸二肝和季戊四醇。 5. The container of claim 4, wherein the fan polyfunctional comonomers are selected from pyromellitic di 曱 liver and pentaerythritol.
6. 权利要求1的容器,其中所迷有效量为氧清除粒子占聚合物重量的至少50ppm。 6. The container of claim 1, wherein the effective amount of fans oxygen scavenging polymer particles account for weight of at least 50ppm.
7. 权利要求1的容器,其中所迷氧清除粒子包含至少一种以下元素:钙、镁、钪、钛、钒、铬、锰、铁、钴、镍、铜、银、锌、锡、 铝、锑、锗、硅、铅、镉、铑或其组合。 7. The container of claim 1, wherein the oxygen-scavenging particles comprise at least fans one of the following elements: calcium, magnesium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, silver, zinc, tin, aluminum , antimony, germanium, silicon, lead, cadmium, rhodium, or combinations thereof.
8. 权利要求1的容器,其中所述氧清除粒子包含至少一种以下元素:钙、镁、钪、钛、钒、铬、锰、铁、钴、镍、铜、银、锌、锡、 铝、锑、锗、硅、铅、镉、铑或其组合。 8. The container of claim 1, wherein said oxygen-scavenging particles comprise at least one of the following elements: calcium, magnesium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, silver, zinc, tin, aluminum , antimony, germanium, silicon, lead, cadmium, rhodium, or combinations thereof.
9. 权利要求2的容器,其中所述氧清除粒子包含至少一种以下元素:4丐、4美、4元、4太、4凡、4备、4孟、纟失、4#、 4臬、4同、4艮、《争、锡、 铝、锑、锗、硅、铅、镉、铑或其组合。 Container of claim 2, wherein said oxygen-scavenging particles comprise at least one of the following elements: 4 beggar, 4 United States, $ 4, 4 too, where 4 4 equipment, 4 Meng Si loss, 4 #, 4 provincial judge 4 with 4 Burgundy, "fight, tin, aluminum, antimony, germanium, silicon, lead, cadmium, rhodium, or combinations thereof.
10. 权利要求3的容器,其中所述氧清除粒于包含至少一种以下元素:钙、镁、钪、钛、钒、铬、锰、铁、钴、镍、铜、银、辞、锡、 铝、锑、锗、硅、铅、镉、铑或其组合。 10. The container of claim 3, wherein the oxygen scavenging particle contains at least one in the following elements: calcium, magnesium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, silver, speech, tin, aluminum, antimony, germanium, silicon, lead, cadmium, rhodium, or combinations thereof.
11. 权利要求l的容器,其中所述氧清除粒子包含铁。 L The container of claim 1, wherein said oxygen-scavenging particles comprise iron.
12. 权利要求l的容器,其中所述氧清除粒子包含铁。 The container of claim l, wherein said oxygen-scavenging particles comprise iron.
13. 权利要求2容器,其中所迷氧清除粒子包含铁。 13. The container of claim 2, wherein the oxygen-scavenging particles comprise iron fans.
14. 权利要求3的容器,其中所述氧清除粒子包含铁。 14. The container of claim 3, wherein said oxygen-scavenging particles comprise iron.
15. 权利要求l的容器,其中所述氧清除粒子包含铁,并且其中所述氧清除粒子的用量占所述成膜聚合物重量的50至12,000 ppm。 The container of claim l, wherein said oxygen-scavenging particles comprise iron, and wherein the oxygen scavenging accounts for the weight of the film-forming polymer particles of 50 to 12,000 ppm.
16. 权利要求1的容器,其中所述聚合物还包含一种或多种选自以下的组份:冲击改性剂、表面润滑剂、脱模剂、稳定剂、结晶助剂、 抗氧化剂、紫外线吸收剂、催化剂钝化剂、着色剂、成核剂、乙醛还原剂、再热还原剂、填充剂、支化剂、'发泡剂和促进剂。 16. The container of claim 1, wherein said polymer further comprises one or more components selected from the following: impact modifiers, surface lubricants, mold release agents, stabilizers, crystallization aids, antioxidants, ultraviolet absorbers, catalyst deactivators, colorants, nucleating agents, acetaldehyde reducing agents, reheat reducing agents, fillers, branching agents, 'blowing agents and accelerators.
17. 权利要求1的容器,其中所述粒子群还包含反应增强粒子。 17. The container of claim 1, wherein the particle group further comprises a reaction reinforcing particles.
18. 权利要求17的容器,其中所述反应增强粒子包括吸湿性物质、电解酸化剂、非电解酸化剂、金属卤化物、金属硫酸盐、金属硫酸氢盐或它们的混合物。 18. The container of claim 17, wherein the reinforcing particles comprise reactive hygroscopic substance, electrolytic acidifying agents, non electrolytic acidifying agents, metal halides, metal sulfates, metal hydrogen sulfate, or mixtures thereof.
19. 权利要求1的容器,其中所述氧清除粒子用至少一种反应增强剂预处理。 19. The container of claim 1, wherein said oxygen-scavenging particles are pretreated with at least one reactive enhancer.
20. 权利要求1的容器,其中所述容器为侧壁厚度为11至25 mil 并且其Hunter雾度值为10%或10%以下的拉伸并瓦。 20. The container of claim 1, wherein said container sidewall thickness is from 11 to 25 mil and is stretching Hunter haze value of 10% or 10% or less, and tiles.
21. 权利要求1的容器,其中所述容器为侧壁厚度为11至25 mil 并且其Hunter雾度值为10%或10%以下的拉伸并瓦。 21. The container of claim 1, wherein said container sidewall thickness is from 11 to 25 mil and is stretching Hunter haze value of 10% or 10% or less, and tiles.
22. 权利要求2容器,其中所述容器为侧壁厚度为11至25 mil 并且其Hunter雾度值为10°/。 22. The container of claim 2, wherein said container is a sidewall 11 to a thickness of 25 mil and has Hunter haze value of 10 ° /. 或10%以下的拉伸瓶。 Or 10% of the stretched bottle.
23. 权利要求3的容器,其中所述容器为侧壁厚度为11至25 mil 并且其Hunter雾度值为10%或10%以下的拉伸瓶。 23. The container of claim 3, wherein said container sidewall thickness is from 11 to 25 mil and has Hunter haze value of 10% or 10% of the stretched bottle.
24. 权利要求l的容器,其中所述聚集区构成容器壁的层压层。 24. The container of claim l, wherein said gathering area constituting the container wall laminate.
25. 权利要求1的容器,其中所述聚集区构成容器壁的共挤出层。 25. The container of claim 1, wherein said gathering area constituting the container wall coextruded layers.
26. 权利要求1的容器,其中所述聚集区的厚度等于容器壁的厚度。 26. The container of claim 1, wherein a thickness equal to the thickness of the aggregate area of the container wall.
27. 权利要求1的容器,其中所述聚集区的厚度小于所述容器壁的厚度。 27. The container of claim 1, wherein the thickness of the aggregate area is less than the thickness of the container wall.
28. 权利要求l的容器,其中所述容器为托盘。 28. The container of claim l, wherein said container is a tray.
Description  Langue du texte original : Chinois

具有低雾度的容器 A container having a low haze

本申请是以下申请的分案申请:申请日:2002年7月25日;申请号:02818680X(PCT/US02/23824);发明名称:"氧清除树脂组合物和具有低雾度的容器以及相关方法,,。 This application is a divisional application of the following applications: Application Date: July 25, 2002; application number: 02818680X (PCT / US02 / 23824); Title: "oxygen-scavenging resin composition and a container having a low haze and related Methods ,,.

技术领域 Technical Field

本发明涉及一种容器。 The present invention relates to a container. 更具体地讲,本发明涉及一种由氧清除树脂组合物制备的容器,所述容器具有低雾度。 More particularly, the present invention relates to a purge vessel by the oxygen in the resin composition, the container having a low haze.

发明背景 Background of the Invention

热塑性树脂如聚对苯二甲酸乙二醇酯(PET)通常用于生产包装材料。 Thermoplastic resins such as polyethylene terephthalate (PET) is typically used in the production of packaging materials. PET在合理条件下加工后产生具有优异阻气特性的高强度制品。 PET under reasonable conditions to produce high strength products have excellent gas barrier properties after processing. 如果暴露于氧气,食物、饮料和药物可能会变质或损坏。 If exposed to oxygen, food, beverages and drugs may be corroded or damaged. 因此为了改善诸如食品、饮料和药品类产品的贮藏保质期以及味道的保留, 用PET提供的阻透保护常常另外添加几层包装材料或加入氧清除剂。 Therefore, in order to improve, such as food, beverage and pharmaceutical products storage shelf life and flavor retention, with PET barrier provides protection often add additional layers of packaging material or added oxygen scavenger.

增加阻气薄膜层祐j人为是被动阻透包装。 Increase the gas barrier film layer woo j man is passive barrier packaging. 例如,由于乙烯-乙烯醇(EVOH)、聚偏二氯乙烯(PVDC)和尼龙MXD6薄膜具有优异的阻氧特性,因此它们通常被用于此目的。 For example, since the ethylene - vinyl alcohol (EVOH), polyvinylidene chloride (PVDC), and Nylon MXD6 films having excellent oxygen barrier properties, they are usually used for this purpose. 然而各层使用不同物料并不优选,因为这样增加包装构造成本并且不能减少包装中已经存在的氧的含量。 However, the use of layers of different materials is not preferred, because it increases the cost of packaging and can not be configured to reduce the amount of packaging existing oxygen.

PET树脂中加入氧清除剂被认为是积极阻透包装。 PET resin is added oxygen scavenger was considered positive barrier packaging. 这种方法对氧敏感产品进行双重保护:包装不但阻止氧从外界进入接触产品, 而且吸收部分在容器中存在以及来自聚合物基质的氧。 This method of oxygen-sensitive products for dual protection: Packaging not only prevents oxygen into contact with the product from the outside, and the absorption of oxygen from the polymer matrix is present within the container as well. 在某些应用中,在包装容器并且紧邻食品放置装有氧清除剂的小袋。 In some applications, the food in the packaging container and disposed adjacent to the sachet containing an oxygen scavenger. 小袋通常限用于固体食品,这种情况下小袋可以很容易与食品分开并且不会 Pouches generally restricted to solid food, in this case the pouch can be easily separated from the food and not

5意外食用。 5 accidental consumption. 生产小袋以及将其引入包装中的烦瑣使得成本增加。 Production and introduction into the pouch packaging cumbersome increased costs.

一种克服使用小袋所带来不便的方法是将清除剂直接加入食品包装壁中。 One way to overcome the inconvenience of using the pouch method is brought scavenger directly into the wall of the food package. 这种加入可以是将清除剂加入整个清除壁或者是将清除剂放置在容器多层侧壁之间的某特定层。 This addition may be added throughout the scavenger wall or remove the scavenger is placed in a particular multi-layer container sidewall. 应该明确的是提及侧壁和壁时也指容器的盖和底部。 It should be clear reference to the sidewall and wall also refer to the lid and bottom of the container. 目前,将清除剂加入整个容器壁的方法用于非透明托盘或包装薄膜中,在这些应用中看不到清除剂。 Currently, the scavenger throughout the container wall, a method for non-transparent trays or packaging films in these applications can not see scavengers. 事实上,任何清除剂都可用于此情况,因为清除剂是不可见。 Virtually any scavenger can be used in this case, because the scavenger is not visible. 然而目前为止,需要透明度的容器仅限于使用在置于容器壁的某单独层时保持透明的有机类清除剂。 So far, however, the need for transparency in the container is limited to the use of transparent when placed in a separate layer of the vessel wall of the organic scavenger. 在单层结构中使用有机清除剂不但受到成本限制,而且因为有机清除剂的性质或清除反应副产物的性质而受到法规的约束。 Organic scavenger in a single-layer structure, not only by cost constraints, but also because of the nature of the organic scavenger or clear the nature of the reaction byproducts and constrained regulations.

使用有机类清除剂的后处理问题是造成成本高的原因。 Use organic scavenger reprocessing issue is the cause of the high costs. 在大多数实施方案中,过渡金属催化剂用于活化可氧化的聚合物。 In most embodiments, a transition metal catalyst for activating the oxidizable polymer. 这种技术的缺点是包装一生产出来就开始与氧反应。 A disadvantage of this technique is that a package produced begins to react with oxygen. 所以,必须立即填装包装瓶。 Therefore, we must immediately fill bottles. 更多清除剂用于补偿在制瓶后至装瓶前的清除能力损失。 More scavenger scavenging for loss compensation until after the bottle before bottling.

在另一种技术中,UV射线用于活化可氧化的聚合物。 In another technique, UV radiation is used to activate an oxidizable polymer. 然而,UV 活化技术相对昂贵,并且引发剂通常不允许用于食品包装。 However, UV-activated technology is relatively expensive, and the initiator is usually not allowed for food packaging. 特别设 Specially designed

计用于啤酒和果汁的包装以防止uv穿透作用,因此uv活化将不能用于那些阻止uv的容器。 Meter for beer and juice packaging in order to prevent the penetration of uv, uv activation therefore will not be used to prevent uv of those containers.

视觉上可接受的有机材料的另一选择是在容器侧壁中使用分散的清除粒子,例如还原性金属粉末。 Alternatively visually acceptable organic material is to use particles dispersed in a clear container sidewall, for example reducing metal powder. 还原性铁粉末通常用于食品包装中清除氧。 Reducing iron powder normally used in food packaging scavenging oxygen. 铁与氧反应形成氧化铁。 Iron reacts with oxygen to form iron oxide. 很多应用也采用盐和水分吸收剂作为反应增强剂以提高铁粉末的反应效率。 Many applications also use salt and moisture absorbers as a reaction enhancer to increase the efficiency of the reaction of iron powder. 因为该反应通常需要水,铁清除组合物保持非活性直到填装包装后,包装内含物的水分迁移入聚合物并与清除组合物接触,开始反应。 Because the reaction usually requires water, the iron scavenging composition remain inactive until after the filled package, the contents of the packaging moisture migration into the polymer and contacts the scavenging composition, to start the reaction.

以前在透明包装中使用清除粉末受到美学,特别是雾度和颜色 Transparent packaging previously used to clear powder by aesthetics, particularly haze and color

的限制。 Restrictions. 通常需要约500-5000 ppm高填充的铁粉以获得足够的氧吸收能力。 Typically requires about 500-5000 ppm iron powder highly filled to obtain sufficient oxygen absorption capability. 常识以及现有技术教导实施者尽量使用最大清除剂表面积, Knowledge and prior art teaches the perpetrators try to use the largest surface area of scavengers,

6这样可提高清除效率和能力,而且铁的使用量最少。 6 This will improve cleaning efficiency and capacity, and the amount of iron in the least. 在实践中,这意味着使用大量微细粒子。 In practice, this means that a large amount of fine particles. 不幸的是,在以前尝试制备用于透明包装的含高浓度细微铁粒子的树脂组合物中得到的包装光学特性很差。 Unfortunately, previous attempts at preparing optical characteristics of transparent packaging for packaging a resin composition containing high concentrations of fine iron particles obtained poor. 这在以任何程度拉伸或取向树脂组合物形成最终制品(例如聚酯瓶)时尤其明显。 This degree when stretched or oriented in any resin composition to form the final product (e.g., PET bottles) in particular. 通常,用这类树脂组合物制备的瓶是半透明的。 Typically, bottles prepared from such resin compositions are translucent. 这些瓶的雾度值通常很高,缺乏透明度。 The haze value of these bottles is usually high, the lack of transparency.

因此,仍需要具有可接受的视觉外观并包含氧清除树脂组合物的包装材料。 Accordingly, the need still having acceptable visual appearance and a resin composition containing oxygen scavenging packaging material. 本发明涉及用于包装和其它应用中的氧清除树脂组合物。 The present invention relates to methods for packaging and other applications, the oxygen-scavenging resin composition. 更具体地讲,本发明涉及具有低雾度的成膜氧清除聚酯树脂组合物。 More specifically, the present invention relates to a film having a low haze oxygen scavenging polyester resin composition. 本发明还涉及具有有效清除氧的功能以及低雾度的容器。 The present invention also relates to a container features and low haze has effectively remove oxygen. 本发明进一步涉及将高浓度氧清除粒子掺入成膜聚酯树脂组合物并使该组合物具有低雾度的方法。 The present invention further relates to a high concentration of oxygen-scavenging particles incorporated into the film-forming polyester resin composition and the composition has a low haze of method.

发明概述 Summary of the Invention

总的来说,本发明提供包含以下组分的树脂组合物:成膜聚酯; 有效量的包含至少一种氧清除组分的氧清除粒子;其中所述粒子具有这样的粒径分布:粒径小于约25nm的粒子不超过以下/>式定义的浓度: In general, the present invention provides a resin composition comprising the following composition: forming polyester; comprising an effective amount of at least one oxygen scavenging oxygen scavenging component particles; wherein the particle has a particle size distribution: particle The particle diameter of less than about 25nm not exceed the following /> is defined concentrations:

ppm = 512.3 xd ppm = 512.3 xd

其中卯m为粒径小于约25 nm的粒子的大致浓度,以ppm重量表示, d为粒径小于约25pm的粒子的表观密度,以g/cn^表示。 Where d m is the particle size is less than the approximate concentration of particles of about 25 nm, expressed in ppm by weight, d is the diameter of less than about 25pm apparent density of particles in g / cn ^ representation.

本发明还包括含以下组分的树脂组合物:成膜聚酯;有效量的氧清除铁粒子,其中所述铁粒子具有这样的粒径分布:粒径小于约25pm的粒子不超过所述树脂重量的约1250 ppm。 The present invention also includes a resin composition containing the following components: a film-forming polyester; an effective amount of oxygen-scavenging iron particles, wherein said iron particles having such a particle size distribution: particle size of less than about 25pm the resin does not exceed weight of about 1250 ppm.

本发明还包括含以下组分的树脂组合物:成膜聚酯以及占树脂重量约50至约2500ppm的铁粒子,其中粒径不超过25nm的铁粒子含量不超过所述树脂重量的约1250 ppm。 The present invention also includes a resin composition containing the following components: a film-forming resin weight polyester and accounted for about 50 to about 2500ppm iron particles, wherein the particle size of not more than 25nm iron particle content is not more than the weight of the resin to about 1250 ppm .

本发明还包括用于形成透明且具有低雾度的制品的聚酯树脂组合物,所述树脂组合物包含占树脂重量约50至约2500ppm的铁粒子, 其中所述透明制品的Hunter (享特)雾度值为约10%或10%以下。 The present invention also includes means for forming a transparent and a polyester resin composition having a low haze article, the resin composition comprises from about 50 to about the resin weight 2500ppm iron particles, wherein said transparent article Hunter (Hunter ) haze value of about 10% or 10% or less.

本发明还包括由含有效量的氧清除粒子的树脂组合物加工而成的制品,其中所述制品的Hunter雾度值为约10%或10%以下。 The present invention further comprises an effective amount of oxygen scavenging particles in the resin composition of the processed article, wherein the article Hunter haze value of about 10% or 10% or less.

本发明提供包含有效量氧清除粒子并且具有低雾度的容器。 The present invention provides removal of particles comprising an effective amount of oxygen and a container having a low haze. 更具体地讲,本发明包括具有至少一个壁的容器,其中所述壁包括聚集区,其中所述聚集区包含成膜聚合物和包含有效量的氧清除粒子的粒子群,其中粒子数量不超过: More specifically, the present invention includes at least one wall of the container, wherein the wall comprises enclave, where the gathering area comprising a film forming polymer and comprising an effective amount of oxygen-scavenging particles particle group, which does not exceed the number of particles :

(6.0xl07粒子+ T)/cm3聚合物其中T为所迷聚集区的厚度,单位为mil (密耳);并且其中所述壁的透射H皿ter雾度最高可为约1%/mil容器壁。 (6.0xl07 particle + T) / cm3 polymer where T is the thickness of the enclave fan units mil (mil); and transmission dish ter haze H wherein the wall can go up to about 1% / mil container wall.

本发明还包括一种将高浓度的氧清除粒子掺混到成膜聚酯树脂组合物并使该组合物具有低雾度的方法,该方法包括以下步骤:提供有效量的包含至少一种氧清除组分的氧清除粒子,其中所述粒子具有这样的粒径分布:粒径小于约25拜的粒子不超过以下公式定义的浓度: The present invention also includes a high concentration of oxygen scavenging particles blended into the film-forming polyester resin composition and the composition has a low haze method, the method comprising the steps of: providing an effective amount of at least one oxygen containing scavenging oxygen scavenging component particles, wherein the particles have such a particle size distribution: particle size of less than about 25 worship particles does not exceed a concentration defined by the following formula:

ppm 512.3 xd ppm 512.3 xd

其中ppm为粒径小于约25 pm的粒子的大致浓度,以ppm重量表示, d为粒径小于约25[im的粒子的表观密度,以g/cms表示;在所述聚酯的一个或多个熔融相聚合加工步骤中、在聚合后造粒前、在聚酯的固态聚合中、在挤塑过程中将所述氧清除粒子加入聚酯树脂组合物中。 Wherein ppm is the approximate concentration of particles of a particle size of less than about 25 pm and the weight expressed in ppm, d is a particle size less than about 25 [im apparent density of the particles in g / cms represents; or one of said polyester a plurality of melt-phase polymerization processing steps, after the polymerization granulation before, in the solid state polymerization of the polyester, in the extrusion process in the oxygen-scavenging particles are added to the polyester resin composition.

本发明还包括包含成膜聚酯和賴:粒的树脂组合物,其中所述孩i 粒具有这样的粒径分布:粒径小于约25pm的粒子不超过以下公式定义的浓度: The present invention also encompasses a film-forming polyester and Lai: grain resin composition, wherein the child i grain has a particle size distribution: particle size of less than about 25pm not exceed a concentration defined by the following equation:

ppm = 512.3 xd ppm = 512.3 xd

其中ppm为粒径小于约25 nm的粒子的大致浓度,以ppm重量表示, d为粒径小于约25pm的粒子的表观密度,以g/cms表示。 Wherein ppm is the approximate concentration of a particle size of less than about 25 nm particles, expressed in ppm by weight, d is the apparent density of a particle size of less than about 25pm particle in g / cms FIG.

8具有可接受的颜色和雾度特征的热塑性树脂组合物很好地克服了现有技术相关的问题。 8 The thermoplastic resin composition have acceptable color and haze characteristics of a good overcomes the problems associated with the prior art. 铁或其它氧清除剂以能够有效清除氧的量存在并且使氧敏感物质有更长的贮藏保质期。 Iron or other oxygen scavenger can effectively remove the amount of oxygen present and the oxygen sensitive materials have longer storage shelf life. 使氧清除剂的粒径达到最佳以提供有效的清除活性,同时降低深色和雾度。 The oxygen scavenger optimum particle size to provide effective scavenging activity, while reducing dark color and haze. 发明详述本发明涉及具有低雾度的成膜氧清除树脂组合物。 DETAILED DESCRIPTION The present invention relates to a low haze film forming oxygen scavenging resin composition. 适用于本发明的热塑性聚合物包括任何热塑性均聚物或共聚物。 Thermoplastic polymers useful in the present invention include any thermoplastic homopolymer or copolymer. 热塑性聚合物的实例包括聚酰胺(例如尼龙6、尼龙66和尼龙612)、线性聚酯(例如聚对苯二曱酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚对苯二曱酸丙二醇酯和聚萘二甲酸乙二醇酯)、支化聚酯、聚苯乙烯、聚^P友酸酯、 聚氯乙稀、聚偏二氯乙烯、聚丙烯酰胺、聚丙烯腈、聚醋酸乙烯酯、 聚丙烯酸、聚乙烯基曱基醚、乙烯-醋酸乙烯共聚物、乙烯-丙烯酸甲酯共聚物、聚乙烯、聚丙烯、乙烯-丙烯共聚物、聚(l-己烯)、聚(4-甲基-l-戊烯)、聚(l-丁烯)、聚(3-甲基-l-丁烯)、聚(3-苯基-l-丙烯)和聚(乙烯基环己烷)。 Examples of thermoplastic polymers include polyamides (e.g., nylon 6, nylon 66, and nylon 612), linear polyesters (e.g., polyethylene glycol esters of terephthalic acid 曱, polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate Yue acid, propylene glycol and polyethylene naphthalate polyethylene terephthalate), branched polyester, polystyrene, poly ^ P Friends esters, polyvinyl chloride, polyvinylidene chloride, polypropylene, polyacrylonitrile, polyvinyl acetate, polyacrylic acid, polyvinyl ether Yue, ethylene - vinyl acetate copolymer, ethylene - methyl acrylate copolymer, polyethylene, polypropylene, ethylene - propylene copolymer, poly (l- hexene), poly (4-methyl -l- pentene), poly (l- butene), poly (3-methyl -l- butene), poly (3-phenyl -l- propylene) and poly (vinyl cyclohexane). 优选用于本发明的热塑性聚合物包括聚酯聚合物或共聚物。 Preferably the thermoplastic polymer used in the present invention comprises a polyester polymer or copolymer. 应当理解的是成膜聚合物是一种能够制成薄膜或片材的聚合物。 It should be understood that the film-forming polymer is a polymer can be formed into a film or sheet. 然而,本发明并不限于薄膜和片材。 However, the present invention is not limited to films and sheets. 本发明容器还包括瓶壁、 托盘、容器底部或盖。 The present invention also includes a sidewall containers, pallets, or bottom of the container lid. 容器壁如吹塑瓶和热成型托盘可以认为是已经加工为容器形状的薄膜或片材,因此也包括在本发明范围内。 Blow bottle as the container wall and thermoformed trays can be considered to have been processed container film or sheet shape, and therefore also included within the scope of the present invention. 本发明聚合物可以通过本领域众所周知的常规聚合方法制备。 Conventional polymerization process of the present invention may be a polymer prepared by known in the art. 聚酯聚合物和共聚物可以通过熔融相聚合制备,所述聚合作用涉及二醇与二羧酸或其相应的酯的反应。 Polyester polymers and copolymers may be prepared by melt phase polymerization, the polymerization reactions involving diols and dicarboxylic acids or corresponding esters. 也可使用由多种二醇和二酸得到的各种共聚物。 You can also use a variety of copolymers from a variety of glycols and diacids obtained. 仅包含一种化学组分的重复单元的聚合物为均聚物。 Only one chemical component comprising repeating units of the polymer is a homopolymer. 在同一大分子中含两种或两种以上化学性质上不同的重复单元的聚合物称为共聚物。 Containing different repeating units of two or more on the chemical nature of the polymer in the same macromolecule called copolymers. 不同的重复单元取决于在最初聚合反应中不同类型的单体数量。 Different repeat units depends on the number of monomers in the first polymerization reaction of different types. 在聚酯的情况下,共聚物包括一种或多种二醇与二酸或多种二酸反应,有时称为三元共聚物。 In the case of polyester, a copolymer comprising one or more diols with a diacid or multiple diacids reactions, sometimes referred to as terpolymers. 合适的二羧酸包括含有约6至约40个碳原子的二羧酸。 Suitable dicarboxylic acids include those containing from about 6 to about 40 carbon atoms and a dicarboxylic acid. 具体的二羧酸包括但不限于对苯二曱酸、间苯二曱酸、萘2,6-二曱酸、环己烷二甲酸、环己烷二乙酸、联苯-4,4'-二曱酸、1,3-苯二氧基二乙酸、 1,2-苯二氧基二乙酸、1,4-苯二氧基二乙酸、丁二酸、戊二酸、己二酸、壬二酸、癸二酸等。 Specific dicarboxylic acids include, but are not limited to, terephthalic acid Yue, Yue isophthalic acid, naphthalene 2,6-Yue acid, cyclohexane dicarboxylic acid, cyclohexane dicarboxylic acid, biphenyl-4,4' two Yue acid, 1,3-phenylene dioxy diacetic acid, 1,2-dioxy phenylene diacetic acid, 1,4-phenylene dioxy diacetic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid and the like. 具体的酯包括但不限于邻苯二曱酸酯和萘二甲酸二酯。 Specific esters include, but are not limited to, phthalic esters and naphthalic Yue diester. 上述酸或酯可以与以下化合物反应:约2至约10个碳原子的脂族二醇、约7至约14个碳原子的脂环族二醇、约6至约15个石1^、 子的芳族二醇或4-10个碳原子的乙二醇醚。 Said acid or ester compound with the following reaction: aliphatic diol from about 2 to about 10 carbon atoms, alicyclic diol from about 7 to about 14 carbon atoms, from about 6 to about 15 stone 1 ^ sub aromatic diols of 4-10 carbon atoms or a glycol ether. 合适的二醇包括但不限于l,4-丁二醇、1,3-丙二醇、1,6-己二醇、1,4-环己烷二曱醇、二甘醇、 间苯二酚和对苯二酚。 Suitable diols include, but are not limited to, l, 4- butylene glycol, 1,3-propanediol, 1,6-hexanediol, 1,4-cyclohexane dimethanol Yue alcohol, diethylene glycol, resorcinol, and Hydroquinone. 也可以使用多官能团共聚单体,通常用量为约Ol至约3%摩尔。 You can also use multi-functional comonomers, generally in an amount of from about Ol to about 3 mol%. 合适的共聚单体包括但不限于偏苯三酸酐、三羟甲基丙烷、均苯四酸二酐(PMDA)和季戊四醇。 Suitable comonomers include, but are not limited to, trimellitic anhydride, trimethylolpropane, pyromellitic dianhydride (PMDA) and pentaerythritol. 也可使用制备酯的多元酸或多元醇。 It can also be prepared using a polybasic acid ester or polyol. 一种优选的聚酯为聚对苯二曱酸乙二醇酯(PET),由约1:1化学计算量的对苯二曱酸或其酯与乙二醇反应制备。 A preferred polyester is polyethylene terephthalate Yue polyethylene terephthalate (PET), from about 1: 1 stoichiometric amount of terephthalic acid or an ester thereof with ethylene glycol Yue acid. 另一种优选的聚酯为聚萘二曱酸乙二醇酯(PEN),由约1:1 - 1:1.6化学计算量的萘二曱酸或其酯与乙二醇反应制备。 Another preferred polyester is polyethylene naphthalate Yue polyethylene terephthalate (PEN), from about 1: 1 - 1: 1.6 stoichiometric amount of naphthalene dicarboxylic acid or an ester thereof with ethylene glycol Yue acid. 另一种优选的聚酯为聚对苯二曱酸丁二醇酯(PBT)。 Another preferred polyester is polyethylene terephthalate, polybutylene terephthalate acid Yue (PBT). 同样优选PET的共聚物、PEN的共聚物和PBT的共聚物。 Also preferred the copolymer PET, PEN copolymers and PBT copolymers. 特别有用的共聚物和三元共聚物为PET与间苯二曱酸或其二酯、2,6-萘二甲酸或其二酯和/或环己烷二曱醇的组合。 Of PET and isophthalic acid or its diester 曱, 2,6-naphthalenedicarboxylic acid, or a combination of di- and / or cyclohexanedicarboxylic 曱 Particularly useful alcohol copolymers and terpolymers. 羧酸或酯与二醇的酯化反应或缩聚反应通常在催化剂存在下进行。 Carboxylic acid esterification reaction or an ester with a diol or polycondensation reaction is usually carried out in the presence of a catalyst. 合适的催化剂包括但不限于氧化锑、三乙酸锑、乙醇酸亚乙酯合锑(antimony ethylene glycolate)、有机4美、氧化锡、醇钬、二月桂酸丁基锡和氧化锗。 Suitable catalysts include, but are not limited to, antimony oxide, antimony triacetate, ethylene co-glycolic acid antimony (antimony ethylene glycolate), organic 4 US, tin oxide, holmium alcohol, dibutyl tin dilaurate and germanium oxide. 上迷催化剂可与锌、锰或镁的醋酸盐或革甲酸10盐联合使用。 The above-described catalysts can be used in combination with zinc, manganese or magnesium acetate or leather formic acid 10 salts. 优选包含锑的催化剂。 Preferably contains antimony catalyst. 另一种优选的聚酯为聚对苯二曱酸丙二醇酯(PTT)。 Another preferred polyester is polyethylene terephthalate Yue acid glycol ester (PTT). 它可通过例如使1,3-丙二醇与至少一种芳族二酸或其烷基酯反应制备。 It can be, for example 1,3-propanediol with at least one aromatic diacid or alkyl ester acid. 优选的二酸和烷基酯包括对苯二甲酸(TPA)或对苯二酸二甲酯(DMT)。 Preferred diacids and alkyl esters include terephthalic acid (TPA) or dimethyl terephthalate (DMT). 因此, PTT优选包含至少约80摩尔百分数的TPA或DMT。 Thus, PTT preferably comprises at least about 80 mole percent of TPA or DMT. 可以共聚成为这样的聚酯的其它二醇包括例如乙二醇、二甘醇、1,4-环己烷二甲醇和1,4-丁二醇。 Copolymerized polyester may be such other diols include for example ethylene glycol, diethylene glycol, 1,4-cyclohexanedimethanol and 1,4-butanediol. 可以同时用于制备共聚物的芳族酸和脂族酸包括例如间苯二甲酸和癸二酸。 Simultaneously aromatic acids and aliphatic acids used to prepare the copolymer include such as isophthalic acid and sebacic acid. 制备PTT的优选催化剂包括钛和锆化合物。 Preferred catalysts for preparing PTT include titanium and zirconium compounds. 合适的催化性钛化合物包括但不限于烷氧基钛及其衍生物、钛络合物盐、含幾基羧酸的钛络合物、二氧化钛-二氧化硅共沉淀物以及水合含碱二氧化钛。 Suitable catalytic titanium compounds include, but are not limited to, alkoxy titanium and its derivatives, titanium complex salts, titanium carboxylate group containing few complexes, titanium dioxide - silicon dioxide coprecipitate and hydrated alkali-containing titanium dioxide. 具体的实例包括钬酸四-(2-乙基己基)酯、钛酸四硬脂酰酯、二异丙氧基-双(乙酰基-丙S同根)合钬、二正丁氧基-双(三乙醇氨基(aminato))合钛、钛酸三丁基单乙酰基酯、钛酸三异丙基单乙酰基酯、四苯甲酸钛、碱性乙二酸钛和丙二酸钛、六氟钛酸钟以及含酒石酸、柠檬酸或乳酸的钛络合物。 Specific examples include holmium tetra - (2-ethylhexyl) ester, tetra stearyl diisopropoxybis - bis (acetyl - S with prop roots) combined holmium, di-n-butyl group - double (triethanol amino (aminato)) titanium, mono acetyl tributyl titanate ester, titanate, mono acetyl triisopropyl ester, benzoic four titanium, titanium alkaline acetic acid and malonic acid titanium, six fluorotitanate bell and titanium complexes containing tartaric acid, citric acid or lactic acid. 优选的催化性钛化合物有四丁氧基钛和四异丙M钬。 Preferred catalytic titanium compounds are titanium tetrabutoxide and tetraisopropyl M holmium. 也可使用相应的锆化合物。 The corresponding zirconium compounds may also be used. 本发明聚合物也可包含能赋予蓝色调的少量含磷化合物(例如磷酸盐)以及催化剂(例如钴化合物)。 The present invention is a polymer capable of imparting a small amount of phosphorus-containing compounds blue tones (e.g., phosphate) and a catalyst (e.g. cobalt compound) may also be included. 上述熔融相聚合反应后可依次进行结晶步骤、固相聚合反应(SSP) 步骤以获得制瓶需要的特性粘度。 After the melt phase polymerization step may be sequentially crystallization, solid phase polymerization (SSP) step to achieve the intrinsic viscosity bottles needed. 结晶和聚合反应可以在分批处理系统的滚筒干燥器中进行。 Crystallization and polymerization can be carried out in a batch processing system the drum dryer. 或者,结晶和聚合反应可以用连续固态方法完成,于是聚合物在各容器中经过预先确定的处理后从一个容器流到另一个容器。 Alternatively, the crystallization and polymerization can be completed by a continuous solid state process, so the pre-determined processing polymers in the vessel after flowing from one container to another. 结晶条件优选温度为约100。 Crystallization conditions are preferably a temperature of about 100. C至约15(TC。固相聚合条件优选温度为约200'C至约232°C,更优选约215'C至约232°C。固相聚合反应可以进行足够长的时间以使特性粘度达到所需的水平,所需的粘度水平取决于具体的应用。对于一般的制瓶应用,优选的特性粘度为约0.65至约1.0分升/克,特性粘度按照ASTMD-4603-86在3(TC 、 60/40重量比的苯酚和四氯乙烷混合物中测定。达到此粘度所需的时间为约8至约21 h。在本发明一个实施方案中,本发明成膜聚合物可以包含回收的聚酯或由回收的聚酯获得的材料(例如聚酯单体、催化剂和低聚物)。本发明提供具有至少一个壁的容器,其中所迷壁包含聚集区。 聚集区包括成膜聚合物和粒子群。有各种技术可将粒子群定位于容器壁的一个区域。例如,如薄膜或壁的接触表面是与所包装产品相邻的表面,最好是使氧清除剂位于接触表面的区域。这些技术的例子包括但不限于层压法、共挤塑法、共注塑法等。能够定位所述粒子群的技术的实例在以下文献中详细阐述:美国专利5,153,038、 6,413,600、 4,525,134、 4,439,493和4,436,778,将各文献全部内容通过引用结合到本文。现在发现使用这些技术可以将高浓度的粒子加入到薄膜或壁中。在本文将粒子群主要定位于其中的局部区域称为聚集区。从包装壁内面至包装壁的外缘,穿过容器壁的横截面,从所述群的笫一个粒子开始到95%的所述群^1计算为止测定聚集区的厚度。 单层薄膜或容器的聚集区厚度为薄膜或容器的厚度。在不为单层的容器壁时,聚集区的厚度将稍微小于壁厚。层压壁的聚集区厚度为含有至少95%粒子群的壁的层的厚度。其中各层在界面融合的多层薄膜或壁中,例如共挤塑形成的多层薄膜或壁,聚集区厚度为包含至少约95%粒子群的层的横截面厚度。在两个或两个以上不同聚集区情况下,聚集区的厚度要减去位于内部和最外面聚集区域之间的一个或多个非聚集区的厚度。这将是ABA结构,其中A包含所^#。聚集区的厚度为A+B+AB。 在为ABAB结构时,聚集区厚度仍为A+B+AB。按照相同的原理, BABAB的厚度为A+B+AB。 ABABA具有3 x A-2 x B的群厚度。12优选聚集区中粒子浓度不超过(6x107粒子+ T)/cm3聚合物,其中T为聚集区的厚度,单位为mil。更优选聚集区粒子浓度不超过(3x107 粒子+ T)/cmS聚合物,其中T为聚集区的厚度,单位为mil。 C to about 15 (TC. Solid phase polymerization conditions preferably at a temperature from about 200'C to about 232 ° C, more preferably from about 215'C to about 232 ° C. Solid phase polymerization can be carried out for a time sufficient to allow the intrinsic viscosity the desired level, the desired viscosity level depends on the particular application. For general applications bottle, preferably an intrinsic viscosity of from about 0.65 to about 1.0 dl / g, an intrinsic viscosity in accordance with ASTMD-4603-86 3 ( TC, 60/40 by weight of phenol and tetrachloroethane mixture Determination time required to reach this viscosity of from about 8 to about 21 h. In one embodiment of the invention, the film-forming polymer of the present invention may comprise recovery or polyester material obtained from recycled polyester (e.g. polyester monomers, catalysts, and oligomers). The present invention provides a container having at least one wall, wherein the wall comprises fans enclave. enclave comprising film forming polymeric composition and particle swarm. Various techniques may be positioned in a region of particle swarm vessel wall. For example, as the contact surface of the film or wall is the surface adjacent to the packaged product, it is preferable that the contact surface is located in an oxygen scavenger Examples of these areas include, but are not limited to, techniques lamination, coextrusion, co-injection molding method and the like can be positioned in the particle group examples of technique detailed in the following documents: U.S. Patent No. 5,153,038, 6,413,600, 4,525, 134, 4,439,493 and 4,436,778, the entire contents of each of which is incorporated herein by reference, and now found that the use of these techniques a high concentration of particles may be added to the film or wall. In this paper, particle swarm mainly located in one of the local area called aggregation area from the inner wall surface of the package to the package wall of the outer edge, a cross section through the container wall, from undertaking of a particle of the group began to 95 percent of the group until the measured thickness calculation ^ 1 gathering area. monolayer film or a gathering area for the thickness of the film thickness of the container or containers in a single layer without the container wall thickness gathering area will be slightly smaller than the wall thickness. enclave wall is the wall thickness of the laminate containing at least 95% of the particle swarm The thickness of the layer multilayer films or walls wherein the layers in the multilayer film or wall interface fusion, for example formed by coextrusion, the thickness of gathering area comprising at least about 95% of the cross-sectional thickness of the layer of particle group in the two Under one or more different enclave, the thickness enclave located subtract or more thickness of a non-clustered area and gathered outside the innermost region. This will be the ABA structure, which contains the A ^ # The thickness of the gathering area of A + B + AB. In the ABAB configuration, the thickness is still gathering area A + B + AB. In the same principle, the thickness BABAB of A + B + AB. ABABA having 3 x A- group thickness 2 x B .12 enclave in particle concentration is preferably not more than (6x107 particle + T) / cm3 polymer, wherein T is the thickness gathering area, the unit is mil. particle concentration is more preferably not more than gathering area (3x107 particles + T) / cmS polymer, wherein T is the thickness of gathering area, in units of mil. 甚至更优选选聚集区粒子浓度不超过(1.5xl(^粒子+ T)/cn^聚合物,其中T 为聚集区的厚度,单位为mil。粒子群包括氧清除粒子以及容器的以分散粒子形式存在的任何其它组分,例如本文中所述的组分。本发明氧清除树脂组合物还包含氧清除粒子。合适的氧清除粒子包含至少一种能够与分子氧反应的可氧化物质。所选的理想物质应不会与氧反应太快以至于不能对其进行加工处理。因此,优选在接触氧时不容易爆炸或燃烧的稳定氧清除物质。从食品安全观点来看,优选低毒性物质,然而有恰当的预防措施时,这就不是限制因素。所述粒子不应该对最终产品的感官特性产生负面影响。优选氧清除粒子包含选自以下的氧清除元素:钙、镁、钪、钛、钒、铬、 锰、铁、钴、镍、铜、锌、银、锡、铝、锑、锗、硅、铅、镉、铑及其组合。更优选氧清除粒子包含选自以下的氧清除元素:钙、镁、 钛、钒、锰、铁、钴、镍、铜、锌或锡。甚至更优选氧清除粒子包含铁。应当理解这些氧清除元素可以以下形式存在:混合物、化合物(例如氧化物或盐)或结合其它元素存在,条件是各氧清除元素能够与分子氧反应。包含至少一种氧清除元素的金属合金同样适合。氧清除粒子可以包含不影响实施本发明的杂质。本领域技术人员已知某些物质能够增强氧清除反应。在本发明优选实施方案中,氧清除粒子用一种或多种促进氧清除反应的反应增强剂预处理。可以使用本领域已知的任何反应增强剂。在本发明一个实施方案中,氧清除粒子包含铁粒子。铁作为氧清除剂与氧反应。可以使用金属铁或合金或包含金属铁的混合物。 此外,应当理解的是金属铁可以包含不影响本发明实施的杂质。可以使用至少三种类型的金属铁粉末:电解铁、海绵铁和羰基13铁。电解铁通过电解氧化铁制备,并且可从例如OM Group, Inc获得退火和未退火形式的电解铁。海绵铁可从例如North American H。ganas, Inc.获得。有至少两种类型的海绵铁:氢还原的海绵铁和一氧化碳还原的海绵铁。羰基铁粉末可从例如Reade Advanced Materials获得。它是用羰基分解法制备。 Even more preferably selected particle concentration gathering area does not exceed (1.5xl (^ particle + T) / cn ^ polymer, wherein T is the thickness of the enclave, the unit is mil. Particle Swarm include oxygen and the removal of particles dispersed particles form the container the existence of any other component, such as the components described herein. oxygen present invention clear resin composition further comprises oxygen scavenging particles. Suitable oxygen-scavenging particles comprise at least one can be oxidized with molecular oxygen in the reaction of the material. Selected The ideal material should not be too quick to react with oxygen to be processed. Therefore, it is preferable not easily explode upon contact or combustion oxygen stable oxygen scavenging material from the food safety point of view, preferably a low toxic substances, However there is proper precautions, this is not a limiting factor of the particles should not adversely affect the organoleptic characteristics of the final product is preferably oxygen-scavenging particles comprise an oxygen scavenging element selected from the following: calcium, magnesium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, tin, aluminum, antimony, germanium, silicon, lead, cadmium, rhodium, and combinations thereof, more preferably selected from oxygen-scavenging particles comprise oxygen-scavenging elements : calcium, magnesium, titanium, vanadium, manganese, iron, cobalt, nickel, copper, zinc or tin and even more preferably oxygen-scavenging particles comprise iron should be understood that these oxygen-scavenging elements may be present in the form of the following: a mixture of the compound (e.g. oxide or a salt thereof) or in combination with other elements are present, with the proviso that each oxygen scavenging elements are capable of reacting with molecular oxygen. oxygen scavenging element comprises at least one metal alloy is also suitable. oxygen scavenging particles may contain impurities without affecting embodiment of the present invention. The skilled certain substances known to be able to enhance the oxygen scavenging reaction. In a preferred embodiment of the present invention, the oxygen scavenging reaction enhancer pretreated with one or more of the particles promote oxygen scavenging reaction. You can use any reaction known in the art to enhance agent. In one embodiment of the invention, the oxygen-scavenging particles comprise iron particles of iron as an oxygen scavenger reacts with oxygen. You can use metallic iron or an alloy or mixture comprising metallic iron. In addition, it should be understood that the metallic iron may contain not Effect of Impurities embodiment of the present invention may be used at least three types of metallic iron powder: electrolytic iron, sponge iron and carbonyl iron 13 electrolytic iron oxide prepared by electrolysis, and available from, for example OM Group, Inc obtain annealed and unannealed form . The electrolytic iron sponge iron is available from, for example North American H.ganas, Inc. There are at least two types of sponge: sponge iron and carbon monoxide, hydrogen reduction sponge iron reduction carbonyl iron powder is available from, for example Reade Advanced Materials It is prepared by decomposition of carbonyl.

根据所选铁的类型,粒子的纯度、表面积和粒子形状可能有很大差异。 Depending on the selected type of iron purity particle surface area and particle shape may vary greatly. 以下所包括典型特征的非限制性的例子说明可能遇到的各种变化形式。 The following features are included typical non-limiting examples illustrate various forms of change that may be encountered. 电解铁以其高纯度和高表面积为大家所熟知,其粒子为树枝状。 Electrolytic iron for its high purity and high surface area is well known that particles are dendritic. tt铁粒子基本为均匀球体,纯度可能高达约99.5%。 tt iron particles are substantially uniform spheres, may be up to about 99.5% purity. 一氧化碳还原的海绵铁的表面积通常为约95平方米每千克(r^/kg),而氢还原的海绵铁的表面积通常为约200 m2/kg。 Surface area of the sponge iron carbon monoxide reduction is usually about 95 square meters per kilogram (r ^ / kg), and the surface area of the sponge iron hydrogen reduction is usually about 200 m2 / kg. 海绵铁可以包含少量的其它元素,例如碳、硫、磷、硅、4美、铝、钬、钒、锰、钙、锌、 镍、钴、铬和铜。 Sponge iron may contain small amounts of other elements, such as carbon, sulfur, phosphorus, silicon, 4 United States, aluminum, holmium, vanadium, manganese, calcium, zinc, nickel, cobalt, chromium and copper.

氧清除粒子以具有足够氧清除能力的有效量存在。 Oxygen scavenging particles having an effective amount sufficient oxygen scavenging capacity exists. 如果氧清除粒子太少,就可能有太多的氧能够穿过容器壁而不会被清除。 If too few oxygen-scavenging particles, it is possible to have too much oxygen to pass through the container wall without being cleared. 足够氧清除能力需要的用量取决于诸如以下的因素:应用的情况、所用聚合物类型、要求阻透保护的气体量、氧清除粒子类型、氧清除粒子的粒径和所包装的产品的水分含量。 A sufficient amount of oxygen scavenging capacity required depends on factors such as the following: the case of application of the polymer type, the amount of gas barrier protection requirements, the oxygen scavenging particle type, oxygen scavenging particle size and moisture content of the packaged product . 优选本发明氧清除容器包含占树脂重量至少约50ppm的氧清除粒子。 Oxygen present invention preferably comprises an amount of epoxy resin purge vessel weight of at least about 50ppm scavenging particles. 甚至更优选本发明氧清除容器包含占树脂重量至少约lOOppm的氧清除粒子。 Even more preferably oxygen present invention comprises from epoxy resin purge vessel weight of at least about lOOppm the removal of particles. 更优选本发明氧清除容器包含占树脂重量至少约500ppm的氧清除粒子。 Oxygen scavenging container of the present invention preferably comprise from about 500ppm epoxy resin weight of at least the removal of particles. 最优选本发明氧清除容器包含占树脂重量至少约lOOOppm的氧清除粒子。 Oxygen scavenging container of the present invention is most preferably comprise from epoxy resin weight of at least about lOOOppm the removal of particles.

发现包含占树脂重量高达约12,000ppm的氧清除粒子(1.2%重量) 的容器(例如薄膜或瓶制品)可具有可接受的雾度特性。 Found to contain up to about 12,000ppm accounting resin weight oxygen-scavenging particles (1.2% by weight) of the vessel (e.g., a film or bottle articles) can have acceptable haze characteristics. 对于雾度不是所关注问题的应用,可理解氧清除粒子或其它粒子的用量可以更高。 The haze is not for the concerns of the application, it is understood the amount of oxygen-scavenging particles or other particles may be higher. 在下文提供实现本发明所必须的粒子群的其它特征。 Necessary to implement the present invention to provide PSO other features below.

本发明组合物可任选还包含一种或多种本领域已知的反应增强剂,以促进氧清除反应。 The compositions of the invention may optionally also contain one or more reaction enhancer known in the art to facilitate the oxygen scavenging reaction. 已知的反应增强剂的例子在美国专利 Examples of known reaction enhancers in U.S. Patent

145,744,056和5,885,481中有阐述,通过引用将其全部内容通过引用结合到本文。 145,744,056 and 5,885,481 have described, by reference in their entirety by reference herein. 合适的试剂包括吸湿性物质、电解酸化剂、非电解酸化剂、金属囟化物、金属硫酸盐、金属硫酸氢盐和各种盐。 Suitable reagents include hygroscopic materials, electrolytic acidifying agents, non electrolytic acidifying agents, metal halides, metal sulfates, metal bisulfate salts and various salts. 反应增强剂可以加入熔融聚合物中或在挤塑时加入。 The reaction enhancers can be added to the molten polymer is added or when the extrusion.

本发明组合物可任选还包含一种或多种选自以下的组份:冲击改性剂、表面润滑剂、脱模剂(denesting agent)、稳定剂、结晶助剂、 抗氧化剂、紫外线吸收剂、催化剂钝化剂、着色剂、成核剂、乙醛还原剂、再热还原剂、填充剂、支化剂、发泡剂、促进剂等。 The composition of the present invention may optionally further comprise one or more components selected from the following: impact modifiers, surface lubricants, mold release agents (denesting agent), stabilizers, crystallization aids, antioxidants, ultraviolet absorbing agents, catalyst deactivators, colorants, nucleating agents, acetaldehyde reducing agents, reheat reducing agents, fillers, branching agents, blowing agents, promoting agents.

应当理解的是如果上述任选组份在树脂内保持其分散性质,则它们也是本文定义的粒子群的一部分。 It should be understood that they are also part of the particle group as defined herein, if the above-mentioned optional components maintain their properties in the resin dispersion.

本发明还涉及将大量粒子加入聚酯树脂组合物并使该組合物具有低雾度的方法。 The present invention also relates to a large number of particles added to the polyester resin composition and the composition has a low haze of method. 所述粒子可与热塑性聚合物在聚合反应期间或之后混合、与聚合物融体混合或与模塑粉末或粒子混合,随后形成注塑制品或者经流延加工成为薄膜或片材。 The thermoplastic polymer particles with the polymerization reaction during or after mixing, or mixed with the polymer melt is mixed with the molding powder or particles, followed by the formation of an injection molded article or processed into cast films or sheets. 因此,所述粒子可以在任何加工步骤中加入,例如在熔融相聚合反应时、熔融相聚合反应后(聚合反应后)但造粒之前、固态聚合反应时以及挤塑时加入。 Thus, the particles may be added at any step in the process, for example, during melt phase polymerization, after the melt phase polymerization reactor was added (post polymerization) but before granulation, extrusion and solid state polymerization reaction. 或者,可以制备氧清除树脂的母粒,然后将其与其它树脂混合或共混。 Alternatively, preparation of oxygen scavenging resin masterbatch, and then mixing or blending with other resins. 优选所述母粒包含相对高含量的粒子,通过母粒与一定量的其它树脂混合或共混达到聚合物产物中所需的粒子浓度。 Preferably, the masterbatch contains a relatively high amount of particles, to achieve the desired particle concentration in the polymer product by mixing other resin or blended with an amount of masterbatch.

本发明氧清除聚酯树脂的优点在于在加工为容器后不但具有氧清除功能而且具有可接受的光学特性。 Clear advantages of oxygen present invention in that the polyester resin is processed into a container only after having oxygen scavenging functionality and acceptable optical properties have. 聚合物的光学特性与结晶度和实际的聚合物结构有关。 The optical properties of polymer crystallinity and the actual polymer structure. 透明度定义为透过样品所能感知的物体的状态。 Transparency is defined as the perception of objects that can be transmitted through the sample state. 透射为光的透射。 Transmitted to the transmission of light. 透明度以未偏离的光来度量。 Transparency to not deviate from light to measure. 换句话说, 透明度是入射光的原有强度减去所有被吸收、散射或通过其它方式损失的光。 In other words, transparency is the original intensity of the incident minus all is absorbed, scattered, or by other means loss of light.

许多聚合物是透明的,但是对可见光透明的聚合物可能因为存在多种添加剂(例如填充剂、稳定剂、阻燃剂、水分和气体)而变得不透明。 Many polymers are transparent, but the polymer may be transparent to visible light due to the presence of various additives (e.g. fillers, stabilizers, flame retardants, water and gas) and becomes opaque. 不透明是因为在这些物质中发生光散射。 Opaque because the light scattering occurs in these substances. 通过所述物质的光 By the light of the substance

15散射降低所观察对象的浅色、深色以及其它有色部分之间的对比度, 在透射影像中产生乳白色状或雾状。 15 to reduce the scattering of light observed object, dark, and contrast between the colored part of the other, resulting in a milky or misty image transmission. 雾度是偏离透射光方向至少2.5 度的光通量的度量。 The haze is a measure of deviation from the transmitted flux of at least 2.5 degrees on the light direction.

聚酯粒子的颜色和亮度可以由视觉观测,也可以通过HunterLab ColorQuest Spectrom改er定量测定。 Color and brightness polyester particles can be observed by a visual determination can be changed er quantified by HunterLab ColorQuest Spectrom. 该4义器使用1976 C正a* 、 M和L* The 4-defined using 1976 C positive a *, M, and L *

颜色和亮度名称。 Color and brightness name. 3*坐标定义一个颜色轴,其中正值朝向色谱的红色端,而负值朝向绿色端。 3 * coordinate defines a color axis, wherein the positive toward the red end of the chromatogram, and negative toward the green end. M坐标定义笫二个颜色轴,正值朝向色谱 M coordinates that define undertaking of two color axis, positive toward chromatography

的黄色端,而负值朝向蓝色端。 Yellow terminal, and negative toward the blue end. LMi增大则说明物质的亮度增强。 LMi increases then the brightness enhancement substances. . 通常,制品(例如瓶或薄膜)的可接受雾度由视觉确定。 Typically, products (such as a bottle or film) determined acceptable by the visual haze. 然而, However,

HunterLab ColorQuest Spectrometer能够定量指出某种制品或树脂的 HunterLab ColorQuest Spectrometer can quantitatively indicate a certain product or resins

雾度。 The haze. 这种定量检测在本文称为透射Hunter雾度。 This quantitative analysis referred to herein as transmission Hunter haze.

本领域已知拉伸薄膜常常比其未拉伸的相应薄膜有更高的雾 Stretched film known in the art often have a higher haze than its unstretched film corresponding

度。 Degrees. 因此,雾度测量值从拉伸和未拉伸的容器壁以及容器本身获得。 Therefore, haze measurements obtained from the stretched and unstretched container walls and the container itself. 本发明容器壁可以包含未拉伸薄膜或片材。 Container wall of the present invention may comprise unstretched films or sheets. 薄膜和片材的制备 Preparation of films and sheets

在本领域中是已知的,众多合适技术中的任意一种都可用于制备薄膜。 Are known in the art, many suitable techniques can be used in any of a preparation of films.

本发明容器也包括用料坯膨胀得到的瓶。 The present invention also includes a container obtained bottle preform expansion. 料坯是用于在模具中膨胀形成瓶的已形成的结构。 Preform is a formed structure has been formed of expanded bottle in a mold. 或者,容器可以包括薄膜、袋装物或其它包装材料。 Alternatively, the container may include films, bags or other packaging materials.

通常,聚酯瓶用吹塑加工法制备,该加工方法通过加热上述料坯至高于聚酯的玻璃化转变温度,将加热的料坯放入所需的瓶状模具中,往料坯中注入空气使其成为模具的形状,然后使模塑瓶从模具脱离转至传送带。 Normally, PET bottle blow molding standby rule of law, the processing method by heating the preform above the polyester glass transition temperature, the heating of blanks into the desired bottle-shaped mold to inject blanks air makes the shape of the mold, and then go to the molded bottle from the conveyor belt from the mold.

在精确测量雾度以及比较雾度值时,必须考虑的两个因素是待测量制品的厚度以及吹塑时间(blow window)。 When accurate measurement of haze and comparing haze value, two factors that must be considered is the thickness of the article to be measured and the blow time (blow window).

为了确定合适的温度以及加工时间以获得最低的雾度值(因为仅与聚酯树脂的结晶过程有关),作出吹塑时间图。 To determine the appropriate temperature and processing time to obtain the lowest haze value (because only about crystallization of the polyester resin), time to blow FIG. 吹塑时间图显示雾度为料坯的加热暴露时间的函数。 Blow time graph shows haze as a preform heating function of exposure time. 通常通过绘制等温线以及将各料 Usually by drawing isotherms and the respective material

16坯在相同温度以不同长短的时间加热而作出吹塑时间图。 16 blanks at the same time heating temperature and different lengths of time to blow FIG. 然后将加热后的料坯拉伸,检测拉伸部分的雾度。 The heated preform is then stretched to detect haze stretching portion. 选择若干不同的温度。 Select a number of different temperatures. 通常, 一种树脂将会有一个产生最低雾度值的最佳温度,采用该温度进行其余的评价。 Typically, a resin will have a best temperature produces the lowest haze value, using the temperature of the rest of the evaluation. 在此描述的操作中,选定一个温度,而变化时间 In this described operation, a selected temperature, and the change time

虽然聚酯具有优异的光学性能,甚至在应力硬化(拉伸)发生结晶时也如此,但是耀:粒添加剂会降低透明度而增加雾度。 While polyester has excellent optical properties, even in the stress hardening (stretching) is also the case when the crystallization takes place, but Yao: granulated additives can reduce the transparency and increase the haze. 粒子数量及其粒径对拉伸及未拉伸的薄膜和制品的雾度都有影响。 The number of particles and particle size on tensile and haze of the unstretched films and articles have an effect. 本领域熟练技术人员能够理解本文公开的热塑性树脂的密度差异很大。 Those skilled in the art will appreciate the difference in density of the thermoplastic resin as disclosed herein greatly. 此外, 粒子群中各种粒子的密度也可能不同。 In addition, the density of particles of various particle populations may be different. 因此,树脂中各种粒子及清除粒子群的优选浓度以粒子数量/树脂体积表达。 Thus, the preferred concentration of various particles and clear to the number of particles Particle Swarm / resin volume expression resins.

应当理解的是在任何粒子群中,各粒子并不是同一粒径,而是包括一个粒径范围。 It should be understood that any particle population, the particles are not all the same diameter, but include a range of particle size. 此外,粒子群中各粒子也可能没有一致的规则形状。 In addition, the particles of each particle group may not be consistent with the rules of shape. 粒子群或粒子群的任何部分可以通过平均粒径描述,通过任何本领域已知的标准技术检测。 Any part or particle swarm particle swarm can be described by an average particle size, standard techniques known in the art to detect any. 这些技术包括粒子在重力影响下在液体中沉降的平衡速率检测、阻力脉冲计数器、光阻断计数器、图像分析器、激光衍射光语以及光子相关光谱。 These techniques include particle sedimentation equilibrium in the liquid under the influence of gravity rate detecting resistance pulse counters, light blocking counters, image analyzers, laser diffraction and photon correlation spectroscopy language. 通常用于描述粒子群 Often used to describe particle swarm

粒径的统计学数值包括:(1)几何平均粒径,是基于对数计算的平均粒径;(2)算术平均值,是基于线性计算的平均粒径;(3)中值粒径, 是分布达50%时的粒径;(4)模式粒径(mode size),分布最多的粒径。 Statistical value particle size include: (1) geometric mean particle size is based on the calculation of the average particle size; (2) the arithmetic mean of the average particle size is calculated based on the linear; (3) the median particle size, Buda is the particle size distribution of 50%; (4) the mode diameter (mode size), the largest particle size distribution. 此外,样品可以通过粒径范围或者小于或等于指定的粒径描述。 In addition, the sample size range or may be less than or equal to the specified particle diameter is described. 这些指标可以通过筛分技术或其它本领域已知的技术确定。 These indicators can be determined by sieving techniques, or other techniques known in the art. 由此,任何特定的粒子群将具有一种粒径分布,这种分布由粒径范围和各粒径的粒子数量来描述。 Thus, any given population of particles will have a particle size distribution that the particle size distribution and the number of particles of each particle size range will be described. 粒径检测技术在以下文献中有详细阐迷:Paul Webb和Clyde Orr, 4w"/Wca/她f/2挂/" F/"e尸crWc/e 7!ec/2Wo/ogy, Micromeritics Instrument Corp. (1997); James PM Syvitski' Pn"c/p/w, Me&油,awe/ 4p!P"ca"0朋o/尸aWc/e 5fee 乂wcr/拜j , Cambridge University Press (1991),两个文献的全部内容都通过引用结合到本 Particle detection techniques are detailed in the following documents explain fans: Paul Webb and Clyde Orr, 4w "/ Wca / she f / 2 hanging /" F / "e corpse crWc / e 7 ec / 2Wo / ogy, Micromeritics Instrument Corp! . (1997); James PM Syvitski 'Pn "! c / p / w, Me & oil, awe / 4p P" ca "0 Four o / dead aWc / e 5fee qe wcr / worship j, Cambridge University Press (1991), the entire contents of both of which are incorporated by reference into the present

17文。 17 messages.

已有各种不同的参数来描述粒子群的粒径。 It has a variety of parameters to describe particle swarm particle size. 例如,能够理解的是粒子大于容器壁的厚度会产生粗糙的表面,因此应该避免大量的 For example, it is possible to understand that the particle is greater than the thickness of the container wall may produce a rough surface, and should avoid a large number of

此类粒子。 Such particles. 通常,优选粒径范围为约1至约70 nm,更优选为约10 至约70 Mm,甚至更优选为约15至约70 jim。 Generally, the preferred particle size range of from about 1 to about 70 nm, more preferably from about 10 to about 70 Mm, even more preferably from about 15 to about 70 jim. 最优选的粒径范围为约20至约70 pm。 The most preferred particle size range of about 20 to about 70 pm. 应当理解上述优选范围仅给出一般性指导,少量粒子的可能在上述范围之外,但是不会影响树脂的本质特性,因此它们也属于本发明法范围。 It should be understood that the above preferred range gives only general guidance, may be outside the above range, but a small amount will not affect the essential characteristics of the resin particles, they also belong to the scope of the present invention method.

如上所述,大量粒子可以加入聚合物中,通过选择粒子群的粒径分布以及控制粒子总数量低于某个最大值从而使对雾度的影响最小。 As described above, a large number of particles may be added to the polymer, the particle size distribution by selecting and controlling the total number of groups of particles below a certain maximum value so that the effect on haze minimized. 所述最大值涉及聚集树脂的厚度并且已经在上文中介绍。 The maximum thickness of the resin involves aggregation and have been described above.

在某些应用中,可能需要进一步控制粒子群的粒径分布以最小化雾度。 In some applications, it may be necessary to further control the particle size distribution of population in order to minimize haze. 这种需要可能取决于包括以下的因素:容器的类型、加工条件以及拉伸比。 This need may depend on factors including the following: the type of container, processing conditions, and stretch ratios. 有利的是,已发现:当氧清除粒子包含铁并且铁的粒径分布为小于或等于约25 pin的粒子不超过树脂重量的约1250ppm时,使用所述含铁热塑性树脂组合物制成的瓶和其它包装材料具有可接受的颜色和雾度特性。 Advantageously, it has been found: When the oxygen-scavenging particles comprise iron and iron the particle size distribution of less than or equal to about 25 pin does not exceed the weight of the resin particles of about 1250ppm, the use of the iron-containing thermoplastic resin composition of the bottle and other packaging materials having acceptable color and haze characteristics. 优选小于约20 fim的铁粒子不超过树脂重量的约800ppm。 Preferably less than about 20 fim iron particles does not exceed the weight of the resin is about 800ppm. 更优选小于约20 pm的铁粒子不超过树脂重量的约500ppm。 More preferably less than about 20 pm iron particles does not exceed the weight of the resin is about 500ppm. 甚至更优选小于约20 pm的铁粒子不超过树脂重量的约100ppm。 Even more preferably less than about 20 pm iron particles does not exceed the weight of the resin is about 100ppm. 理想的是小于约10 pm的铁粒子不超过树脂重量的约800ppm。 Preferably less than about 10 pm iron particles does not exceed the weight of the resin is about 800ppm. 更理想的是小于约10 nm的铁粒子不超过树脂重量的约500ppm。 More preferably less than about 10 nm iron particles does not exceed the weight of the resin is about 500ppm. 甚至更理想的是小于约10 nm的铁粒子不超过树脂重量的约100ppm。 Even more preferably less than about 10 nm iron particles does not exceed the weight of the resin is about 100ppm. 优选小于或等于约5 pm的铁粒子不超过树脂重量的约500ppm。 Preferably less than or equal to about 5 pm iron particles does not exceed the weight of the resin is about 500ppm. 更优选小于或等于约5 pm的铁粒子不超过树脂重量的约100ppm。 More preferably less than or equal to about 5 pm iron particles does not exceed the weight of the resin is about 100ppm. 因此,应当理解的是整个说明书和权利要求书的叙述"小于约25 [im"已包括20 pm、 10 Hm、 5 jim以及小于5 |im的更小铁粒子粒径,这取决于优选的粒径。 Thus, it should be understood that the book's narrative throughout the specification and claims, "is less than about 25 [im" included 20 pm, 10 Hm, 5 jim and less than 5 | im smaller iron particle size, depending on the preferred grain Trail. 类似地,叙述"不超过约1250ppm" 已包括800ppm、 500ppm以及100ppm的更小用量,这取决于优逸的 Similarly, the narrative "of no more than about 1250ppm" included 800ppm, 500ppm and 100ppm smaller amount, depending on the superior Yi

18用量。 18 dosage. 应理解的是粒予大于用所述高铁含量热塑性树脂组合物制造的瓶或其它包装材料厚度时,可能产生粗糙表面,因此应该避免大量这样的大粒子。 It should be understood that when grain to more than bottles or other packaging material thickness by the high iron content of the thermoplastic resin composition may produce a rough surface, and therefore should avoid a large number of such large particles.

更一般地讲,有利的氧清除粒子的粒径分布为粒子表观密度的函数。 More generally, it is advantageous oxygen scavenging particle size distribution of particles in the apparent density. 因为粒子内度的多孔性,金属粉末粒子的密度不一定与制造该粉末的材料的密度完全一致。 Because of the porous particles, the density of the metal powder particle is not necessarily identical with the density of the powder producing material. 表观密度是指单位体积松散粉末的重量,通常表达为克每立方厘米(g/cm3)。 Apparent density refers to the weight per unit volume of loose powder, usually expressed in grams per cubic centimeter (g / cm3). 确定其表观密度的粉末特性在以下文献中有论述:Peter K. Johnson, "Powder Metallurgy", OAwer Ewc^c/opecZ/ao/ C/^Tm'ca/ rec/wo/ogy, §§4.1, 4.2 (1995)。 Powder characteristics determine its apparent density are discussed in the following documents: Peter K. Johnson, "Powder Metallurgy", OAwer Ewc ^ c / opecZ / ao / C / ^ Tm'ca / rec / wo / ogy, §§4.1 , 4.2 (1995). Johnson报导铁粒子的典型表观密度值为约O.97至约3.4 g/cm3。 Johnson reported that iron particles typical value of about O.97 to the apparent density of about 3.4 g / cm3. 当使用包含铁或其它物质的粒子时,该粒子的有利粒径分布通过以下公式确定。 When the particles containing iron or other material, favorable particle size distribution of the particles is determined by the following formula.

优选氧清除粒子具有这样的粒径分布:小于或等于约25 的粒子不超过以下公式定义的浓度: Preferably the oxygen-scavenging particles have such a particle size distribution: less than or equal to about 25 particles does not exceed a concentration defined by the following formula:

ppm = 512.3 xd ppm = 512.3 xd

其中卯m为粒径小于约25 的粒子的大致浓度,以ppm重量表示, d为粒径小于约25拜的粒子的表观密度,以g/cn^表示。 Where d m is the approximate concentration of particle size less than about 25 ppm by weight to represent, d is the diameter of less than about 25 thanks to an apparent density of particles in g / cn ^ representation. 前面公式的常数512.3是基于一种粒径分布计算得到的,这样小于或等于约25 的粒子的浓度不超过1250ppm重量,其中所述粒子的表观密度为约2.44 g/cm3。 512.3 the previous formula is based on a constant particle size distribution calculated, so the concentration of particles of less than or equal to about 25 weight does not exceed 1250ppm, wherein the apparent density of the particles is about 2.44 g / cm3.

更优选氧清除粒子具有这样的粒径分布:小于或等于约20 的粒子不超过以下公式定义的浓度: More preferably the oxygen scavenging particles have such a particle size distribution: less than or equal to about 20 particles does not exceed a concentration defined by the following equation:

ppm = 327.9 xd ppm = 327.9 xd

其中ppm为粒径小于约20 的粒子的大致浓度,以ppm重量表示, d为粒径小于约20 nm的粒子的表观密度,以g/cn^表示。 Wherein ppm is the approximate concentration of particles of a particle size less than about 20 ppm by weight to represent, d is the particle diameter of less than about 20 nm of the apparent density in g / cn ^ representation. 常数327.9 以及以下7>式中的各常数按照前面公式中的相同方法确定。 7 and the following constants 327.9> wherein each of the constant is determined according to the same manner as in the preceding formula.

甚至更优选氧清除粒子具有这样的粒径分布:小于或等于约20 pm的粒子不超过以下公式定义的浓度: Even more preferably the oxygen scavenging particles have such a particle size distribution: less than or equal to about 20 pm particles does not exceed a concentration defined by the following formula:

ppm = 204.9 xd ppm = 204.9 xd

19其中ppm为粒径小于约20 nm的粒子的大致浓度,以ppm重量表示, d为粒径小于约20 urn的粒子的表观密度,以g/cn^表示。 Wherein the particle size of less than 19 ppm is the approximate concentration of particles of about 20 nm, expressed in ppm by weight, d is the diameter of less than about 20 urn apparent density of particles in g / cn ^ representation.

更优选氧清除粒子具有这样的粒径分布:小于或等于约20 的粒子不超过以下公式定义的浓度: More preferably the oxygen scavenging particles have such a particle size distribution: less than or equal to about 20 particles does not exceed a concentration defined by the following equation:

ppm = 41.0 xd ppm = 41.0 xd

其中ppm为粒径小于约20 的粒子的大致浓度,以ppm重量表示, d为粒径小于约20 ^im的粒子的表观密度,以g/cn^表示。 Wherein ppm is the approximate concentration of particles of a particle size less than about 20 ppm by weight to represent, d is the diameter of less than about 20 ^ im apparent density of particles in g / cn ^ representation.

理想的氧清除粒子具有这样的粒径分布:小于或等于约10 的粒子不超过以下公式定义的浓度: Oxygen-scavenging particles preferably has a particle size distribution: less than or equal to about 10 particles does not exceed a concentration defined by the following equation:

ppm = 327.9 xd ppm = 327.9 xd

其中ppm为粒径小于约10 fim的粒子的大致浓度,以ppm重量表示, d为粒径小于约10 的粒子的表观密度,以g/cmS表示。 Wherein ppm is the approximate concentration of a particle size of less than about 10 fim particles, expressed in ppm by weight, d is the apparent density of the particles of a particle size of less than about 10 to g / cmS FIG.

更理想的氧清除粒子具有这样的粒径分布:小于或等于约10pm 的粒子不超过以下公式定义的浓度: More preferably such oxygen-scavenging particles have a particle size distribution: less than or equal to about 10pm particles does not exceed a concentration defined by the following equation:

ppm = 204.9 xd ppm = 204.9 xd

其中ppm为粒径小于约10 的粒子的大致浓度,以ppm重量表示, d为粒径小于约10拜的粒子的表观密度,以g/cn^表示。 Wherein ppm is the approximate concentration of particles of a particle size less than about 10 ppm by weight to represent, d is the diameter of less than about 10 thanks to an apparent density of particles in g / cn ^ representation.

甚至更理想的氧清除粒子具有这样的粒径分布:小于或等于约10 的粒子不超过以下公式定义的浓度: Even more preferably such oxygen-scavenging particles have a particle size distribution: less than or equal to about 10 particles does not exceed a concentration defined by the following equation:

ppm = 41.0 xd ppm = 41.0 xd

其中ppm为粒径小于约10 的粒子的大致浓度,以ppm重量表示, d为粒径小于约10拜的粒子的表观密度,以g/cn^表示。 Wherein ppm is the approximate concentration of particles of a particle size less than about 10 ppm by weight to represent, d is the diameter of less than about 10 thanks to an apparent density of particles in g / cn ^ representation.

优选氧清除粒子具有这样的粒径分布:小于或等于约5 pm的粒子不超过以下公式定义的浓度: Preferably the oxygen-scavenging particles have such a particle size distribution: less than or equal to about 5 pm particles does not exceed a concentration defined by the following equation:

ppm = 204.9 xd ppm = 204.9 xd

其中ppm为粒径小于约5 pm的粒子的大致浓度,以ppm重量表示, d为粒径小于约5 的粒子的表观密度,以g/cms表示。 Wherein ppm is the approximate concentration of a particle size of less than about 5 pm particles, expressed in ppm by weight, d is the apparent density of the particles of a particle size of less than about 5 to g / cms FIG.

更优选氧清除粒子具有这样的粒径分布:小于或等于约5 [im的粒子不超过以下公式定义的浓度: More preferably oxygen scavenging particles have such a particle size distribution: less than or equal to about 5 [im particles does not exceed a concentration defined by the following formula:

20<formula>formula see original document page 21</formula> 20 <formula> formula see original document page 21 </ formula>

其中ppm为粒径小于约5 fim的粒子的大致浓度,以ppm重量表示, d为粒径小于约5 pm的粒子的表观密度,以g/cms表示。 Wherein ppm is the approximate concentration of a particle size of less than about 5 fim particles, expressed in ppm by weight, d is the apparent density of a particle size of less than about 5 pm particles in g / cms FIG.

本发明还提供一种包含以下组分的树脂组合物:成膜聚酯;微粒;其中所述樣W立具有这样的粒径分布:小于约25 pm的粒子不超过以下公式定义的浓度: The present invention also provides a resin composition comprising the following component composition: a film-forming polyester; microparticles; W wherein the sample stand having such a particle size distribution of: less than about 25 pm particles does not exceed a concentration defined by the following formula:

ppm= 512.3 xd ppm = 512.3 xd

其中ppm为粒径小于约25 的粒子的大致浓度,以卯m重量表示, d为粒径小于约25pm的粒子的表观密度,以g/cr^表示。 Wherein ppm is the approximate concentration of particles of a particle size of less than about 25 weight expressed in d m, d is the apparent density of a particle size of less than about 25pm particle in g / cr ^ expressed. 所述孩M立可以包含或不包含氧清除元素。 M The child may or may not contain stand oxygen scavenging elements. 合适的微粒包括但不限于陶瓷微粒、 塑料微粒、金属微粒、分子篩等。 Suitable microparticles include, but are not limited to, ceramic particles, plastic particles, metal particles, zeolite and the like.

通过以下方法将大量粒子加入到容器壁并使其具有低雾度:提供粒子群;选择所述粒子群的粒径分布以包含合适量的具有优选粒径范围的粒子;在一个或多个以下加工步骤将所述粒子群加入聚合物中,形成聚合物与粒子的混合物:聚合物的熔融相聚合反应;聚合反应后并在造粒前;聚合物的固态聚合反应;挤塑;然后将所述聚合物和粒子的混合物加工为具有至少一个壁的容器。 By the following method a large number of particles are added to the container wall and it has a low haze: providing a particle group; selecting the particle size distribution of the particle group to contain a suitable amount of particles having the preferred size range; in one or more of the following said step of processing the polymer particle group added to form a mixture of polymer and particles: polymer melt phase polymerization; after polymerization and before pelletizing; solid state polymerization of the polymer; extrusion; then the processing said mixture of polymer and particles having at least one wall of the container.

如上所迷,通过不同的工艺,可将粒子群定位于容器壁的一个或多个聚集区。 As described above, through different processes, particle swarm may be located in one or more of the aggregate area of the container wall. 在本实施方案中,聚集区包含聚合物和粒子的混合物,并且加入方法还包括将所述混合物与另外的聚合物混合以形成具有聚集区和至少一个其它区域的壁的步骤。 In the present embodiment, the accumulation area comprising a mixture of polymer and particles, and the method further comprises the added mixture with additional polymer to form an aggregate having at least one wall region and the other region. 所述另外的聚合物可以是相同或不同的聚合物,但是不含任何清除剂。 The additional polymer may be the same or different polymer, but without any scavenger.

本发明的具有低雾度的氧清除树脂可以流延加工为聚合物薄膜领域通常采用的任何厚度的未拉伸薄膜或片材。 Oxygen has a low haze clear resin of the present invention can be processed into a non-stretched cast film or sheet of any thickness typically employed a polymer film art.

在一个优选实施方案中,薄膜的厚度至少为约0.5 mil,并且透射Hunter雾度值优选小于约10%,更优选小于约8%,甚至更优选小于约5%。 In a preferred embodiment, the thickness of the film is at least about 0.5 mil, and the transmission Hunter haze value of preferably less than about 10%, more preferably less than about 8%, even more preferably less than about 5%. 虽然雾度值高于不包含氧清除粒子或其它粒子的聚酯样品, 但是上迷雾度值完全在许多商业应用中可接受值的范围内。 Although the haze value higher than the polyester sample does not contain oxygen-scavenging particles or other particles, but the exact value in the range of the fog in many commercial applications of acceptable values.

21本发明的具有低雾度的氧清除树脂可以拉伸成瓶,其中所有瓶 Oxygen has a low haze of 21 invention remove resin can be stretched into a bottle, which all bottles

的侧壁厚度为约9至约35 mil,优选约11至约25 mil,更优选约14 至约21 mil。 The sidewall thickness of about 9 to about 35 mil, preferably from about 11 to about 25 mil, more preferably from about 14 to about 21 mil.

在一个优选实施方案中,所有瓶的侧壁厚度为约14至约21 mil, 并且在最佳吹塑时间的条件下,瓶的Hunter雾度值优选小于约10%, 更优选小于约8%,甚至更优选小于约5%。 In one preferred embodiment, all of the bottle sidewall thickness is about 14 to about 21 mil, and in the best conditions blow time, bottle Hunter haze value is preferably less than about 10%, more preferably less than about 8% , even more preferably less than about 5%. 虽然雾度值高于不包含铁粒子或其它粒子的氧清除组合物的聚酯样品,但是上述雾度值完全在许多商业应用中可接受值的范围。 Although the haze value higher than the polyester sample does not contain iron particles or other particles of oxygen-scavenging compositions, but above the haze value in the range of many commercial applications entirely acceptable values.

确定上述粒子的最大优选粒子浓度,以使未拉伸薄膜具有小于约1%的结晶度。 Determining a maximum particle concentration of the particles is preferably such that an unstretched film having less than about 1% crystallinity. 通常,随着聚合物树脂结晶度增加,雾度随之增加。 Typically, the crystallinity of the polymer resin increases, haze increases. 因此,能够理解在具有更高结晶度的聚合物组合物中粒子的最大优选浓度将降低。 Therefore, it is possible to understand in the polymer composition having a higher crystallinity maximum preferred concentration of particles will be reduced.

为了说明本发明的操作性,制备了以下实施例并按照以下通用试验方法部分的描述测试。 To illustrate the operability of the present invention, the following examples were prepared and tested in accordance with the following general description of test methods section. 但是,实施例不应该被看作是对本发明范围的限制。 However, the examples should not be construed as limiting the scope of the invention. 权利要求用于对本发明进行限定。 Used in the present invention defined by the claims.

通用试验方法制备实施例1-26 PET共聚物树脂通过美国专利5,612,423公开的方法制备,将其全部内容通过引用结合到本文。 Common test methods for preparation of Example 1-26 PET copolymer resin disclosed in U.S. Patent 5,612,423 for preparing the implementation of the entire contents of which are incorporated herein by reference. 获得具有不同粒径的铁粒子样品。 Iron particles obtained samples with different particle sizes. 购自Pyron的氢还原海绵铁用于实施例1-10。 Available from Pyron hydrogen reduction sponge iron used in Example 1-10. 从ISP Technologies获得的to铁粉末用于实施例11-26。 To iron powder obtained from ISP Technologies used in Example 11-26. 因此,用于实施例3的铁粒子的粒径范围为约25至约38 pm。 Thus, for example iron particles size range of the third embodiment is about 25 to about 38 pm. 应当理解的是这样的样品可以通过例如筛选获得。 It should be appreciated that such a sample can be obtained for example by screening. 使用双螺杆挤出机计量加料器将铁粒子加入聚酯树脂, 得到含2.5%重量铁的树脂母粒(含铁树脂组合物)。 Using a twin screw extruder feeder weighing machine iron particles are added to the polyester resin to obtain a resin masterbatch containing 2.5% by weight of iron (iron resin composition). 将此母粒与基础 This masterbatch with the base

树脂共混获得所需的浓度。 Resin blend to obtain the desired concentration. 将基础树脂/铁混合物在325。 The base resin / iron mixture at 325. F(163。C)真空干燥18 h。 F (163.C) vacuum drying 18 h. 将干燥树脂转移到Nissei ASB 50T Injection Blow-Moiding机的Novotec干燥料斗。 The dried resin is transferred to a Novotec drying hopper Nissei ASB 50T Injection Blow-Moiding machine. 将料斗加热至325下(163。C),设置露点为-40。 The hopper was heated to 325 under (163.C), set a dew point of -40. F(-40。C)。 F (-40.C).

分两步加工,制备瓶的料坯并吹塑成瓶。 A two-step process to prepare the bottle preform and blown into bottles. 首先,用Mini-jector 或Nissei机器制备料坯。 First, Mini-jector or Nissei machine prepared blank. 然后,在Cincinnati Milacron Reheat Blow Lab (RHB-L)吹塑机将料坯吹塑为瓶。 Then, in Cincinnati Milacron Reheat Blow Lab (RHB-L) blow molding machines will be expected to blow the bottles. 在Mini-jector制备料坯时采用以下条件:循环时间45秒,注射时间15秒,后端加热器温度270。 When Mini-jector preform prepared using the following conditions: 45 seconds cycle time, injection time of 15 seconds, the temperature of the rear end of the heater 270. C,前端加热器温度275°C,喷嘴加热温度275°C。 C, the front end of the heater temperature 275 ° C, the heating temperature of the nozzle 275 ° C. 注射压力为约1000至约1500 psig。 Injection pressure of about 1000 to about 1500 psig. Milacron RHB-L烤箱温度为约163。 Milacron RHB-L oven temperature of about 163. C至约177。 C to about 177. C。 C. 暴露时间为约31至约52秒。 Exposure time of about 31 to about 52 seconds.

穿过变薄、拉伸部分的瓶侧壁进行雾度检测。 Through thin, stretched bottle sidewall portions were detected haze. 因为这些检测采用整个瓶,所以实际厚度包括两个侧壁。 Because these were detected by whole bottle, so the actual thickness of the two side walls. 使用HunterLab ColorQUEST Sphere Spectrophotometer System,并配置IBM PS/2 Model 50Z计算机,IBM Proprinter II点阵打印机,各类样品夹具,绿色、灰色和白色的校正板以及光阱。 Use HunterLab ColorQUEST Sphere Spectrophotometer System, and configure the IBM PS / 2 Model 50Z computer, IBM Proprinter II dot matrix printer, various sample holder, green, gray and white calibration plate and a light trap. HunterLab Spectrocolorimeter积分球传感器是一种颜色及外观检测仪。 HunterLab Spectrocolorimeter integrating sphere sensor is a color and appearance of the detector. 灯光被积分球散射,从目标物体穿过(透射) 或反射至透镜。 Integrating sphere scattered light from the target object through (transmitted) or reflected to the lens. 透镜聚集光线,将光线导向衍射光栅,将光分散为其构成波长。 Lens gather light, the light guide diffraction grating for light dispersion wavelength constitution. 分散的光被反射到硅二极管阵列。 Scattered light is reflected into a silicon diode array. 二极管的信号穿过放大器到达转化器,被处理产生数据。 Diode signal arrives through an amplifier converter, to generate data to be processed. 雾度数据由软件提供。 Haze data is provided by the software. 该数据是计算所得散射光透射率与总透射率的比乘以100得到"雾度%" (0%为透明材料,100%为不透明材料)。 The data is calculated scattered light transmittance and total transmittance multiplied by 100 to get "Haze%" (0% transparent material, 100% an opaque material). 为检测透射率或反射率准备 Ready to detect transmission or reflectance

的样品必须干净并且没有任何表面刮痕或磨损。 The sample must be clean and free from any surface scratches or wear. 样品大小必须与所述球体开口的几何尺寸一致,在检测透射率时,样品大小受限于分隔间的尺寸。 Sample size must be consistent with the geometry of the sphere opening and in the detection of the transmittance, the sample size is limited by the size of the compartments. 测试所有样品的四个不同的位置,例如瓶侧壁或代表性的薄膜区域。 Four different positions all tested samples, e.g., a bottle sidewall or representative film area of.

Panametrics Magna誦Mike 8000 Hall Effect Thickness Gauge用于检测瓶侧壁的厚度。 Panametrics Magna chanting Mike 8000 Hall Effect Thickness Gauge for detecting bottle sidewall thickness. 小钢球置于受试材料的一侧,磁性探针在下面。 Small ball is placed on one side of the test material, the magnetic probe below. 球与探针的距离通过Hall效应传感器检测。 Distance between the ball and the probe is detected by a Hall effect sensor. 更具体地讲,采用配置DPU-411热感打印机(II型)、远程脚踏开关、靶球工具包以及Standard 801PRProbe的Magna-Mike8000。 More specifically, the use of configuration DPU-411 thermal printer (II type), remote foot switch, a target ball kit and Standard 801PRProbe the Magna-Mike8000. 测量两次,然后平均。 Measure twice, and then averaged.

23铁粒子浓度、平均铁粒径以及在约11至约13 mil恒定样品厚度和最佳吹塑时间条件下的雾度值总结于表1和表2中。 23 iron particle concentration, particle size and the average iron haze at about 11 to about 13 mil sample thickness constant and optimal conditions for blow molding time values are summarized in Table 1 and Table 2. 对比实施例1 、 6和11不包含铁粒子。 Comparative Examples 1, 6 and 11 do not contain iron particles. 表1报告的铁粒子粒径由供货商提供。 Table 1 reports the iron particle size provided by the supplier. 检测得到的表2的铁粒子粒径是基于体积的几何平均值。 Detection resulting table 2 iron particle size is based on the geometric mean of the volume. 表l Table l

拉伸的聚酯薄膜组合物中的铁粒子 Stretched polyester film composition iron particles

实施例编号Fe浓度粒径最佳再热时间雾度(%) Example No. Fe concentration optimal particle reheat time of haze (%)

(ppm) (sec) (Ppm) (sec)

1 0 - 43 1.5 10--43 1.5

2 1250 °25 49 7.56 2 1250 ° 25 49 7.56

3 1250 25-38 49 4.53 3125025-3849 4.53

4 1250 38-45 52 4.58 4125038-4552 4.58

5 1250 45-75 52 4.41 5125045-7552 4.41

6 0 — 43 1.5 60--43 1.5

7 2500 °25 46 14.08 7 2500 ° 25 46 14.08

8 2500 25-38 46 9.13 8250025-3846 9.13

9 2500 38-45 46 8.45 9250038-4546 8.45

10 2500 45-75 40 8.56 10250045-7540 8.56

25拉伸的聚酯薄膜组合物中的铁粒子和雾度 25 stretched polyester film composition of iron particles and haze

表2 Table 2

施例编 Fe浓度 粒径(Mm) 粒子数 最佳再热 雾度(%) Example Code Fe concentration diameter (Mm) optimal number of particles reheat haze (%)

—, (ppm) (xlOs)/cni3 聚合物 时间(sec) -, (Ppm) (xlOs) / cni3 polymer time (sec)

11 0 - 0 43 1.5 90.89 110--043 1.5 90.89

12 雨 3.23 0.3729 46 5.1 89.78 Rain 12 46 5.1 3.23 0.3729 89.78

13 250 3.23 0.9324 40 6.98 88.66 13 250 40 6.98 3.23 0.9324 88.66

14 500 3.23 1.8647 46 9.12 86.17 14 500 46 9.12 3.23 1.8647 86.17

15 800 3.23 2.9836 46 11.63 83.99 15 800 46 11.63 83.99 3.23 2.9836

16 1000 3.23 3.7295 46 16.44 78.1 161 000 46 16.44 78.1 3.23 3.7295

17 100 4.787 0.0750 49 4.55 89.76 17100 49 4.55 4.787 0.0750 89.76

18 250 4.787 0.1875 49 6.74 89.73 18 250 4.787 0.1875 6.74 89.73 49

19 500 4.787 0.3750 46 9.04 88.27 19 500 4.787 0.3750 9.04 88.27 46

20 800 4.787 0.5999 46 11.8 87.21 20 800 46 11.8 87.21 4.787 0.5999

21 画 4,787 0.7499 46 12.99 83.68 Videos 4,787 0.7499 21 46 12.99 83.68

22 100 7.819 0.0483 49 5.4 90.51 22100 49 5.4 7.819 90.51 0.0483

23 250 7.819 0.1207 46 6.85 89.83 23 250 7.819 0.1207 6.85 89.83 46

24 500 7.819 0.2415 43 8.49 88.79 24500 43 8.49 7.819 0.2415 88.79

25 800 7.819 0.3864 49 7.83 88.06 25 800 7.819 0.3864 7.83 88.06 49

26 1000 7.819 0.4830 46 8.81 87.27 261 000 46 7.819 0.4830 8.81 87.27

制备实施例27-32 实施例27至32也是如上制备的拉伸薄膜样品。 Preparation Example stretched film samples of Examples 27-32 is 27-32 prepared above embodiment. 结果在表3中列出。 The results are listed in Table 3. 用于实施例27-29的铁类型是未退火的电解铁,基于体积的几何平均粒径为约10.84 pm。 Example 27-29 for an iron type is not annealed electrolytic iron, based on the geometric volume average particle diameter of about 10.84 pm. 用于实施例30-32的铁为一氧化碳还原的海绵铁,基于体积的几何平均粒径为约18.61〖im。 Iron used in the examples 30-32 was carbon monoxide reduction sponge iron, based on the geometric volume average particle diameter of about 18.61 〖im. 虽然聚合物中铁的浓度(ppm重量)相当,但是每立方厘米聚合物的粒子数量随着粒径的减小而增多,透射Hunter雾度/mil薄l^度也随之降低。 Although the polymer concentration of iron (ppm by weight) quite, but the number of particles per cubic centimeter polymer increase with decreasing particle size and transmission Hunter haze / mil thin l ^ degree decreases. 应该注意的是对于实施例27-32,雾度检测仅采用瓶侧壁,不采用整个瓶。 It should be noted that for Example 27-32, the haze is detected using only the bottle sidewall, do not use the entire bottle.

26表3 26 Table 3

粒径、粒子数量以及雾度的变化<table>table see original document page 27</column></row> <table>制备实施例33-44 为了研究未拉伸树脂中不同粒径粒子的最佳浓度,用Haake搅拌机制备薄膜。 Changes in particle size, the number of particles and the haze of <table> table see original document page 27 </ column> </ row> <table> Preparation Example 33-44 unstretched resin in order to study the different optimal particle size concentration was prepared films Haake mixer. 在几个1加仑容器中各称量加入2500.0 g HiPERTUF 89010共聚聚酯树脂,在完全真空的真空烘箱中于约IO(TC干燥过夜。 In each of several 1 gallon vessel was added weighed 2500.0 g HiPERTUF 89010 copolyester resin, in a vacuum oven at full vacuum at about IO (TC dried overnight.

将真空状态恢复为大气压下的氮气气氛。 The vacuum restore nitrogen atmosphere at atmospheric pressure. 在氮气气氛下称量合适量的ISP Technologies制备的羰基型铁粉末,^v若干小瓶,获得所需的不同浓度。 Under a nitrogen atmosphere carbonyl-type iron powder weighing an appropriate amount of the preparation ISP Technologies, ^ v plurality of vials, to obtain different desired concentrations. 供货商提供的标称粒径范围为约7至约9 pm。 The nominal size range Supplier of about 7 to about 9 pm. 该铁粉基于体积的几何平均粒径为约7.819 pm。 The iron-based geometric volume average particle diameter of about 7.819 pm. 在从烘箱取出热树脂之前立即将铁加入树脂中,密封各小瓶,将混合物在辊炼冲几共混约5 min。 Before removing the hot resin from the oven and immediately the iron added to the resin, each vial was sealed, and the mixture was blended in a mill punch a few about 5 min. 将共混后混合物加入用于生产薄膜的Haake Polylab挤出系统的加料斗。 Haake Polylab After blending the mixture was added for the production of thin-film extrusion hopper system. 树脂在挤出机中熔融,从模头挤出形成平板片。 Resin melted in an extruder, extruded from the die forming the sheet. 将薄的、 未取向的基本无定形薄膜进料通过控制温度的3辊抛光机,骤冷以最大程度减少结晶,并且获得最终抛光的表面。 The thin, unoriented, substantially amorphous film by controlling the temperature of the feed roll polishing machine 3, quenched to minimize crystallinity and to obtain the final polished surface. 将冷却的薄膜绕在巻轴上。 The cooled film wound in Volume axis. 表4中列出了具有恒定铁浓度的典型薄膜样品的薄膜厚度(mil)、 %透射Hunter雾度以及。 Table 4 lists the typical film having a film thickness of samples of a constant concentration of iron (mil),% transmittance and a Hunter haze. /。 /. 雾度/mil。 Haze / mil. 实施例33和34的铁浓度为约0.9659x 106粒子/cm3聚合物,实施例35-37的铁浓度为约2.8978 x 1(^粒子/cm3聚合物。可以看出虽然雾度随薄膜厚度增加而增加, 但是每mil薄,度的雾度却保持恒定。在实施例38-44中,薄膜的厚度保持为约11 mil不变,但改变每立方厘米聚合物的粒子数量。可以看出每mil厚度的雾度随粒子浓度升高而增加。 Examples 33 and iron concentrations of about 34 embodiment 0.9659x 106 particles / cm3 polymer, Example 35-37 iron concentration is from about 2.8978 x 1 (^ particles / cm3 the polymer can be seen that although the haze increases with film thickness increase, but each thin mil, haze degree was kept constant. In Example 38-44, the thickness of the film was about 11 mil maintained constant, but changing the number of particles per cubic centimeter polymer can be seen that each haze mil thickness increases with increasing particle concentration.

表4 Table 4

雾度与聚集区厚度(T)的关系实施例编号Fe浓度(ppm) 厚度T 雾度(%) 雾度/mil (Ppm) thickness T haze (%) Haze / mil Example No. Fe Concentration haze and aggregation area thickness (T) implementation

(mils) (Mils)

33 2000 11 2.17 0.197 33,200,011 2.17 0.197

34 2000 15 3.07 0.205 34,200,015 3.07 0.205

6000 6000

35 6000 11 5.29 0.481 35,600,011 5.29 0.481

36 6000 15.3 6.68 0.437 366 000 15.3 6.68 0.437

37 6000 20 8.78 0.439 37,600,020 8.78 0.439

表5 Table 5

雾度与粒子数量的关系实施例编Fe浓度(ppm) 粒子数量厚度T 雾度/mil 号(xl()6)/cm3聚(mils) Code Fe concentration cases haze and relational implementation of the number of particles (ppm) Number of particle thickness T haze / mil resolution (xl () 6) / cm3 poly (mils)

合物 Compound

38 0 0 10 0.035 380 010 0.035

39 1000 0.483 11 0.127 391 000 11 0.127 0.483

40 2000 0.9659 11 0.197 402 000 0.9659 11 0.197

41 3000 1.4489 11 0.302 413 000 1.4489 11 0.302

42 6000 2.8978 11 0.481 426 000 2.8978 11 0.481

43 10000 4.8297 11 0.745 4,310,000 4.8297 11 0.745

44 12000 5.7956 10,7 0.880 4,412,000 5.7956 10.7 0.880

如表1所示,当铁粒子粒径大于约25 nm时,雾度值也小于10%, 甚至在铁浓度达2500 ppm时也小于10%。 As shown in Table 1, when the iron particle size of greater than about 25 nm, the haze value is less than 10%, even when the iron concentration of 2500 ppm is less than 10%. 在含l"0 ppm铁以及"00 Containing l "0 ppm iron as well as" 00

28卯m铁时,在平均粒径小于或等于约25 即分别为实施例2和7的情况,产生最高雾度值。 When 28 d m iron, in an average particle size of less than or equal to about 25 namely the case of Example 2 and 7 embodiment, producing the highest haze value. 然而,当铁粒子粒径小于或等于约25pm,在铁含量高达约12500 ppm时所得雾度值仍小于10%。 However, when the iron particle size of less than or equal to about 25pm, when the iron content of up to about 12500 ppm resulting haze value is still less than 10%. 如表2所示,当铁粒子粒径小于或等于约9 fim时,在铁含量为约800卯m时所得雾度值小于10%。 As shown in Table 2, when the iron particle size of less than or equal to about 9 fim, the iron content of the resulting haze of about 800 d m value is less than 10%. 此外,当铁粒子粒径小于或等于约5 pm时,在铁含量为约500 ppm时所得雾度值小于10%。 In addition, when the iron particle size of less than or equal to about 5 pm, when the iron content of about 500 ppm is the proceeds of a haze value of less than 10%.

当粒子群在聚合物中的浓度(ppm重量)恒定时,每立方厘米聚合物的粒子数量随粒径增加而减少,如表3所示。 When the particle swarm concentration (ppm by weight) in the polymer is constant, the number of particles per cubic centimeter polymer increase with the particle size decreases, as shown in Table 3. 整体透射H皿ter雾度随样品厚度的增加而增加,但是每mil厚度的雾度保持相对恒定,如表4所示。 H ter dish overall transmittance haze with increasing thickness of the sample increases, but the haze per mil thickness remains relatively constant, as shown in Table 4. 在每立方厘米聚合物的粒子浓度高达(6 xlO?粒子+ T)时,得到的每mil容器壁雾度值小于1.0%,其中T为聚集区的厚度(mil),如表5所示。 In the polymer particle concentration per cubic centimeter up (6 xlO? Particles + T), the wall haze per mil of the container obtained value less than 1.0%, where T is the thickness (mil) gathering area, as shown in Table 5.

现在应该理解的是,本发明通过提供包含有效量氧清除粒子并且具有可接受的颜色和雾度特征的组合物克服了现有技术有关的难题。 Now it should be understood that the present invention by providing oxygen-scavenging particles comprising an effective amount and composition have acceptable color and haze characteristics to overcome the problems related to the prior art. 所得的树脂可以用于形成透明瓶、薄膜以及其它容器和包装材料。 The resulting resin may be used to form transparent bottles, films, and other containers and packaging materials. 这些材料包含可有效清除氧的量的氧清除粒子,使氧敏感物质有更长的贮藏包质期。 These materials contain an effective amount of oxygen scavenging oxygen scavenging particles, the oxygen sensitive materials have a longer shelf package Shelf. 此外,这些材料具有可接受的雾度特征。 In addition, these materials have acceptable haze characteristics.

虽然已经根据专利法规阐述了最佳模式和优选实施方案,但是本发明的范围并不受此限制,而是由所附权利要求书规定。 Although the described preferred embodiments and the best mode in accordance with the Patent Statutes, the scope of the present invention is not so limited, but rather that defined by the appended claims. 因此,本发明包括落入本发明权利要求书范围的所有改进或变化。 Accordingly, the present invention fall within the claims of the invention includes the scope of all modifications or variations.

29 29

Citations de brevets
Brevet cité Date de dépôt Date de publication Déposant Titre
US503425228 mars 199023 juil. 1991Plm AbOxygen barrier properties of pet containers
US57440567 juin 199528 avr. 1998Amoco CorporationOxygen-scavenging compositions and articles
US575965314 déc. 19942 juin 1998Continental Pet Technologies, Inc.Oxygen scavenging composition for multilayer preform and container
US580423626 sept. 19968 sept. 1998Frisk; PeterOxygen scavenging container
US608358523 sept. 19964 juil. 2000Bp Amoco CorporationOxygen scavenging condensation copolymers for bottles and packaging articles
Classifications
Classification internationaleC08K3/24, C08L67/00, C08K3/22, C08K3/10, C08J5/00, C08K5/34, C08K3/34, C08J3/22
Classification coopérativeB29C55/02, B29C47/1027, B29C47/0007, C08K2201/005, C08K3/08, C08J2367/02, C08J3/203, C08K3/34, C08K3/22, Y10T428/1359, Y10T428/1355, Y10T428/1397, Y10T428/1352
Classification européenneC08K3/34, C08K3/22
Événements juridiques
DateCodeÉvénementDescription
12 juil. 2006C06Publication
6 sept. 2006C10Entry into substantive examination
24 févr. 2010C14Grant of patent or utility model
26 oct. 2011ASSSuccession or assignment of patent right
Owner name: MULTISORB TECHNOLOGIES, INC.
Free format text: FORMER OWNER: M + G POLIMERI ITALIA SPA
Effective date: 20110914
26 oct. 2011C41Transfer of patent application or patent right or utility model